JPH0573231B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field to which the invention pertains] The present invention relates to a photoreceptor member having a photoconductive layer made of amorphous silicon having silicon atoms as a matrix, and a surface protection layer having particularly excellent properties is provided on the photoconductive layer. The present invention relates to a light receiving member suitable for an electrophotographic photoreceptor. [Description of the Prior Art] Conventionally, light-receiving members used in electrophotographic photoreceptors, etc., have superior consistency in their photosensitivity regions compared to other types of light-receiving members, and
For example, JP-A No. 54-86341 and JP-A No.
Amorphous material (hereinafter referred to as "a-Si (H, Receiving members are attracting attention. By the way, such a light-receiving member is
When the photoconductive layer is made of a-Si (H, In addition, in order to improve the moisture resistance, continuous repeated usage characteristics, electrical pressure resistance, usage environment characteristics, durability, etc. of the photoconductive layer, and to obtain stable image quality over a long period of time, the photoconductive layer is It is known to provide a surface protective layer on. The surface protective layer is required to efficiently exhibit the various functions described above, and therefore various non-single-crystalline materials having high resistance and sufficient light transmittance, that is, amorphous materials are used. or/
and polycrystalline materials have been proposed, and it is known that one of these proposals is to use a thin film composed of an amorphous material containing boron nitride (hereinafter referred to as "a-BN"). . (Refer to JP-A-59-12448 and JP-A-60-61760.) However, when a thin film composed of a-BN is used as a surface protective layer, sometimes the a-BN
Thin films deteriorate due to various mechanical damages, including corona discharge during charging treatment and contact with other members, such as cleaning blades, and cannot maintain the aforementioned various functions required of surface protective layers. There is a problem in that it becomes impossible to demonstrate performance over a period of time. In addition, the photoreceptive member using the a-BN thin film has insufficient charging ability, and when forming an image using such a photoreceptor, the image quality deteriorates, such as ghosting on the image. There is also the problem that it may appear as follows. [Object of the Invention] The present invention solves the above-mentioned problems related to the surface protective layer of a light-receiving member used in an electrophotographic photoreceptor, etc., and provides an improved product that exhibits a desired function over a long period of time. The main object of the present invention is to provide a light-receiving member having a surface protective layer. Another object of the present invention is to provide a light-receiving member for use in electrophotographic photoreceptors and the like, which has stable charging ability at all times and can provide images of excellent quality over a long period of time. [Structure of the Invention] The present inventors have conducted extensive research in order to solve the above-mentioned problems related to the surface protective layer of a light-receiving member used in an electrophotographic photoreceptor, etc., and to achieve the above-mentioned object of the present invention. By stacking the layers, we found that the structure of the BN thin film used as the surface protective layer was an important factor. That is, two types of structures are known for boron nitride single crystals: a hexagonal system in which the coordination number of the constituent elements is 3, and a cubic system in which the coordination number of the constituent elements is 4. The present inventors continued to study how the structure of boron nitride affects when a thin film composed of boron nitride is used as a surface protective layer of a light-receiving member used in an electrophotographic photoreceptor. It was found that boron nitride of any structure cannot be used as a surface protective layer, and that boron nitride of a structure with a specific coordination number is suitable. In other words, hexagonal crystals with a coordination number of 3 have the same structure as graphite, are very soft, and have a Mohs hardness of 2, so when used as a surface protective layer, corona discharge It is vulnerable to the impact of active substances such as ions, ozone, and electrons generated by
Furthermore, it has been found that deterioration occurs due to various mechanical damages such as contact with a cleaning blade or the like. On the other hand, those with a cubic structure in which the coordination number of the constituent elements is 4 were found to have high hardness and sufficient resistance to corona discharge and mechanical impact. . Therefore, from the standpoint of strength alone, it is preferable that the surface protective layer be made of an amorphous material containing boron nitride with a four-coordinate structure. By the way, image formation using electrophotography consists of steps such as corona charging of the light-receiving member, image exposure, development with toner, transfer to paper, and cleaning of the light-receiving member. , the surface of the light-receiving member comes into contact with members made of different materials. As a result, the quality of the image transferred onto paper is greatly influenced by the quality of the contact between the members used in each process and the surface of the light-receiving member. For example, as an example,
Considering the cleaning process using a blade,
If the surface of the light-receiving member is too hard, the blade will wear out quickly, making cleaning failures more likely. Additionally, the lifespan of the blade is shortened, which increases the cost of maintaining the copier. On the other hand, if the surface of the light-receiving member is too soft, the surface of the light-receiving member will be easily scraped by the blade, the formed image will have many image defects, and the life of the light-receiving member will be shortened. Moreover, the cost of maintaining copiers increases. In this way, the surface hardness of the light-receiving member must be determined by taking into consideration the balance with the hardness of the various members that come into contact with it in various processes. When used as a surface protective layer of a light-receiving member, further improvements are required for each member of each process of image formation by electrophotography. Based on these findings, the present inventor conducted further research and found that when a non-single-crystal material containing a mixture of boron nitride with a four-coordinate structure and boron nitride with a three-coordinate structure is used as a surface protective layer. It has been found that it is possible to obtain an electrophotographic light-receiving member having a surface hardness that is well balanced with the various members used in each process. The present invention was completed based on this knowledge, and its main points are: a support;
A photoreceptive layer comprising, on the support, at least a photoconductive layer made of an amorphous material based on silicon atoms and containing at least one of hydrogen atoms and halogen atoms, and a surface protective layer. In the light-receiving member comprising: In the light receiving member. The light-receiving member provided by the present invention is characterized by its surface protective layer, and the support as well as other constituent layers including the photoconductive layer may be arbitrarily selected depending on the purpose of use. be able to. Therefore, a typical example of the layer structure of the light-receiving member of the present invention will be described below, with reference to a case where the light-receiving member of the present invention is used for electrophotography, but the light-receiving member of the present invention is not limited thereto. 1A to 1A are diagrams schematically showing typical examples of the layer structure of the light-receiving member of the present invention for use in electrophotography. In the example shown in FIG. 1A, a photoconductive layer 102 and a surface protective layer 103 are provided in this order on a support 101, and the surface protective layer 103 covers the free surface 10.
7. In the example shown in FIG. 1B, a charge injection blocking layer 104, a photoconductive layer 102, and a surface protection layer 103 are provided in this order on a support 101. In the example shown in FIG. 1C, a long wavelength light absorption layer 105, a photoconductive layer 102, and a surface protection layer 103 are provided in this order on a support 101. The example shown in FIG.
are arranged in this order. The example shown in FIG. 1E includes a charge injection blocking layer 104,
Adhesion layer 106, photoconductive layer 102 and surface protection layer 1
03 are provided in this order, and the example shown in 1F is one in which a long wavelength light absorption layer 105, an adhesion layer 106, a photoconductive layer 102, and a surface protection layer 103 are provided in this order. In the example shown in FIG. 1G, a long wavelength light absorption layer 105, a charge injection blocking layer 104, a photoconductive layer 102, and a surface protection layer 103 are provided in this order on a support 101. Wavelength light absorption layer 1
05 and the charge injection blocking layer 104 can also be changed. In the example shown in FIG. 1H, a long wavelength light absorption layer 105, a charge injection blocking layer 104, an adhesion layer 106, a photoconductive layer 102 and a surface protection layer 103 are provided on a support 101.
are arranged in this order. In the example shown in FIG. 1I, a charge injection blocking layer 104, a photoconductive layer 102, an intermediate layer 10,
8 and the surface protective layer 103 are provided in this order. The support 101 used in the light receiving member of the present invention is
It 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 Pb, and alloys thereof. Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide, glass, ceramic, and paper. It is preferable that at least one surface of these electrically insulating supports is conductively treated, and a light-receiving layer is 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, InO ₃ , ITO (In ₂ o ₃ +Sn), etc., or if it is a synthetic resin film such as polyester film, it can be made of NiCr, Al, Ag, Pb, Zn. , Ni, Au, Cr,
A thin film of metal such as Mo, Ir, Nb, Ta, V, Tl, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the above metal to make the surface conductive. give gender. The shape of the support can be a plate, an endless belt, a cylinder, etc. with a smooth surface or an uneven surface.
The thickness is determined as appropriate to form a desired light-receiving member, but if flexibility as a light-receiving member is required, the thickness must be within a range that can fully demonstrate its function as a support. can be made as thin as possible. However, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more. In the light receiving member of the present invention shown in FIG. 1B,
A charge injection blocking layer 104 provided between the support 101 and the photoconductive layer 102 prevents electrons from being injected into the photoconductive layer 102 from the support side when the photoconductive layer 102 is subjected to charging treatment. The charge injection blocking layer 104 is a layer provided for hydrogen or polycrystalline silicon (hereinafter referred to as "poly-Si (H,
X)". ), or so-called non-single crystal silicon containing both (hereinafter referred to as "Non-Si (H,
X)". ) [Note that what is commonly called microcrystalline silicon is classified as a-Si. ] contains an atom belonging to group of the periodic table (hereinafter simply referred to as a "group atom") or an atom belonging to a group of the periodic table (hereinafter simply referred to as a "group atom") It is made up of things. Specifically, the group atoms contained in the charge injection blocking layer 104 include B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl.
(thallium), etc., but particularly preferred are B and Ga. In addition, specific examples of group atoms include P (phosphorus), As (arsenic), and Sb.
(antimony), Bi (bismuth), etc. can be used, but P and As are particularly preferred.
The amount of group group atoms or group atoms contained in the charge injection blocking layer 104 is 3 to 5×10 ⁴ atomic.
ppm, preferably 50 to 1×10 ⁴ atomic ppm, 1
It is desirable to set it as x10 ^<2> -5*10 ^<3> atomic ppm. Further, the amount of halogen atoms or hydrogen atoms contained in the charge injection blocking layer 104 is 1×10 ³ to 7×
10 ⁵ atomic ppm, preferably 1×10 ³ to 2× especially when composed of poly-Si(H,X)
10 ⁵ atomic ppm, and in the case of a-Si(H,X), it is preferably 1×10 ⁴ to 6×10 ⁵ atomic ppm. Further, the thickness of the charge injection blocking layer 104 of the light receiving member of the present invention is preferably 0.03 to 15μ, preferably 0.04 to 10μ, and optimally 0.05 to 8μ. In the light receiving member of the present invention shown in FIG. 1C,
The long wavelength light absorption layer 105 provided between the support 101 and the photoconductive layer 102 is made of Non-Si (H,X) containing at least one of germium atoms (Ge) and tin atoms (Sn). When long wavelength light such as a laser beam is used as an exposure light source, the long wavelength light absorption layer 105 efficiently absorbs the long wavelength light that cannot be completely absorbed by the photoconductive layer 102. This has a function of significantly preventing interference phenomena caused by reflection of long wavelength light on the surface of the support 101. The amount of Ge atoms, the amount of Sn atoms, or the sum thereof contained in the long wavelength light absorption layer 105 is 1 to 1.
10 ⁶ atomic ppm, preferably 1×10 ² to 9×
10 ⁵ atomic ppm, more preferably 5×10 ² to 8×
It is desirable to set it to 10 ⁵ atomic ppm. Further, the amount of hydrogen atoms or halogen atoms contained in the long wavelength light absorption layer 105 is preferably 1×10 ³ to 3
×10 ⁵ atomic ppm is desirable, especially
In the case ^of poly-Si ( ^Ge , Sn) (H,
In the case of Sn) (H, X), preferably 1×10 ⁴ to 6×
It is desirable to set it to 10 ⁵ atomic ppm. Furthermore, the layer thickness of the long wavelength light absorption layer 105 in the light receiving member of the present invention is 0.05 to 25μ, preferably 0.07μ.
~20μ, optimally 0.1~15μ. In the light receiving member of the present invention shown in FIG. 1D,
The adhesive layer 106 provided between the support 101 and the photoconductive layer 102
Non-Si is a layer that functions to improve the adhesion with 2 and contains at least one type selected from oxygen atoms, carbon atoms, and nitrogen atoms.
(H,
X)”. ). The amount of oxygen atoms, carbon atoms, and nitrogen atoms contained in the adhesive layer 106, or the sum of at least two of them, is 100 to 9×10 ⁵ atomic ppm, preferably 100 to 4×10 ⁵ atomic ppm. It is desirable to do so. Further, the amount of hydrogen atoms or halogen atoms contained in the adhesive layer 106 or the sum thereof is preferably 10 to 7×10 ⁵ atomic ppm,
Especially in the case of poly-Si(O,C,N)(H,X)
10～2× ¹⁰⁵ atomic ppm, a-Si (O, C, N)
In the case of (H, X), 1×10 ³ to 7×10 ⁵ atomic
It is desirable to set it to ppm. Incidentally, the charge injection blocking layer 104, the long wavelength light absorption layer 105, and the adhesion layer 106 in the light receiving member of the present invention can be used in combination, and the first example shows a typical example thereof.
They are figures E to H. Furthermore, in the light-receiving member of the present invention, at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms is contained in the charge injection blocking layer 104 or the long wavelength light absorption layer 105, so that these layers have a It is also possible to have the function as an adhesion layer, and the long wavelength light absorption layer 105
By containing group atoms or group atoms therein, or by containing germanium atoms or tin atoms in the charge injection blocking layer 104, a layer having the functions of both of these layers can be obtained. Incidentally, the charge injection blocking layer 104, the long wavelength light absorption layer 105, and the adhesion layer 106 in the light receiving member of the present invention are composed of a material based on Non-Si (H, X), but poly-Si There are various methods for forming a layer composed of (H,X), including the following methods. One method is to set the substrate temperature to a high temperature, specifically 400 to 450℃, and place plasma on the substrate.
This method involves depositing a film using the CVD method. Another method is to first form an amorphous film on the surface of a substrate, that is, to form a film by plasma CVD on a substrate whose temperature is about 250°C, and then annealing the amorphous film. This is a method of The anealing treatment is performed by heating the substrate to 400 to 450° C. for about 20 minutes or by irradiating it with laser light for about 20 minutes. The photoconductive layer 102 of the light receiving member of the present invention is a-
A layer composed of Si (H, X) or a-Si (Ge, Sn) (H, At least one selected from oxygen atoms, carbon atoms, and nitrogen atoms can be contained. Halogen atoms contained in the photoconductive layer 102
Specific examples of (X) include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. and photoconductive layer 10
The amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in 2, or the sum of the amounts of hydrogen atoms and halogen atoms (H+X) is preferably 1 to 40 atomic
%, more preferably 5 to 30 atomic %. Further, the purpose of containing group atoms or group atoms in the photoconductive layer 102 is to control the conductivity of the photoconductive layer 102. As such group atoms and group atoms, the same atoms as those contained in the charge injection blocking layer 104 described above can be used;
2, the charge injection blocking layer 10
4 contains a substance of opposite polarity to that contained in the charge injection blocking layer 104, or contains a substance of the same polarity as that contained in the charge injection blocking layer 104 in an amount much smaller than that contained in the layer 104. You can force it. The amount of group atoms or group atoms contained in the photoconductive layer 102 is preferably 1×10 ⁻³ to 1×
10 ³ atomic ppm, more preferably 5×10 ⁻² to 5×
10 ² atomic ppm, optimally 1×10 ^-1 to 2×
It is desirable to set it to 10 ² atomic ppm. The purpose of containing at least one selected from oxygen atoms, carbon atoms, and nitrogen atoms in the photoconductive layer 102 is to increase the dark resistance of the photoconductive layer 102 and to improve the film quality of the photoconductive layer 102. The goal is to improve. And photoconductive layer 10
The amount of such atoms contained in 2 is preferably 1×10 ^-3 to 50 atomic%, more preferably 2×
10 ^-3 ~40 atomic%, optimally 3×10 ^-3 atomic%
It is desirable to do so. Furthermore, at least one of germanium atoms (Ge) and tin atoms (Sn) can be contained in the photoconductive layer 102, but the purpose of containing such atoms is to improve sensitivity to long wavelength light such as laser light. In this case, the amount of these atoms contained in the photoconductive layer 102 is preferably 1 to 9.5×10 ⁵ atomic.
It is desirable to set it to ppm. Furthermore, in the light-receiving member of the present invention, the layer thickness of the photoconductive layer is one of the important factors for efficiently achieving the object of the present invention, and is one of the important factors for imparting desired characteristics to the light-receiving member. Therefore, it is necessary to pay sufficient attention when designing the light-receiving member.
100μ, preferably 3 to 80μ, optimally 5μ
~50μ. The surface protection layer 103, which is a feature of the light-receiving member of the present invention, is provided on the photoconductive layer 102 described above and has a free surface 107. The surface protective layer 103 has various characteristics required for a light-receiving member, such as moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics,
It not only improves durability and the like, but also functions to prevent charges from being injected into the photoconductive layer 102 from the free surface 107 side when the photoreceptive layer is subjected to charging treatment. Surface protective layer 10 of the light-receiving member of the present invention
3 is a non-single crystal material containing a mixture of boron nitride having a four-coordinate structure and boron nitride having a three-coordinate structure [hereinafter referred to as "Non-BN". ], that is, a polycrystalline material [hereinafter referred to as "poly-BN". ] or amorphous material [written as “a-BN”. 〕and
It is composed of a mixture with poly-BN,
Furthermore, at least one of a hydrogen atom or a halogen atom can be contained [hereinafter,
It is written as "Non-BN(H,X)". ] Regarding the ratio of each atom constituting the surface protective layer 103, the following conditions are satisfied, when the composition ratio of Non7BN (H, X) is expressed as (B _x N _1-x ) _1-y (H, X) _y It is desirable that you satisfy the following. For x; 0.1≦x≦0.9, preferably 0.2≦x≦0.8, optimally 0.3≦x≦0.7 For y; 0.004≦y≦0.4, preferably 0.005≦y≦0.3,
Optimally 0.01≦y≦0.2 In the light receiving member of the present invention, the surface protective layer 1
The layer thickness of 03 is also one of the important factors for efficiently achieving the purpose of the present invention, and is determined appropriately depending on the desired purpose, but the thickness of the constituent atoms contained in the surface protective layer It is necessary to determine the amount based on mutual and organic relationships depending on the properties required for the surface protective layer. Furthermore, it is also necessary to consider economic efficiency, which takes into account productivity and mass production. For these reasons, the layer thickness of the surface protective layer 103 of the light receiving member of the present invention is preferably 0.003 to 30μ,
More preferably 0.004-20μ, optimally 0.005-10μ
It is. Furthermore, in the light-receiving member of the present invention, an intermediate layer 108 may be formed between the above-mentioned surface protective layer 103 and photoconductive layer 102. The intermediate layer 108
is a-Si(H,X) containing carbon atoms or
The intermediate layer 108 is composed of poly-Si (H,
It is desirable to set it to 85 atomic%, optimally 40 to 80 atomic%. Further, the amount of hydrogen atoms (H), the amount of halogen atoms (X), and the amount of hydrogen atoms + halogen atoms (H+X) contained in the intermediate layer 108 are preferably 1 to 70 atomic%, more preferably 2 to
It is desirable to set it to 65 atomic%, optimally 5 to 60 atomic%. Furthermore, the layer thickness of the intermediate layer 108 is preferably 0.003 to 30 μm, more preferably 0.004 to 30 μm.
It is desirable that the thickness be 20 μm, most preferably 0.005 to 10 μm. Next, a method for forming the constituent layers of the light-receiving member of the present invention will be explained. The amorphous material constituting the light receiving member of the present invention is
Both are glow discharge methods (low frequency CVD, high frequency
AC discharge CVD such as CVD or microwave CVD, or DC discharge CVD, etc.), sputtering method, vacuum evaporation method, ion plating method, optical CVD method,
It can be formed by various thin film deposition methods such as thermal CVD. These thin film deposition 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 light-receiving member to be created. The glow discharge method or the sputtering method is preferred because it is relatively easy to control the conditions for manufacturing the light-receiving member, and halogen atoms and hydrogen atoms can be easily introduced together with silicon atoms. suitable. Further, the discharge method and the sputtering method may be used together in the same system. For example, by glow discharge method, 4-coordination structure and 3-coordination structure
In order to form a surface protective layer composed of Non-BN (H, A raw material gas for N supply that can supply atoms (N) and a raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as necessary are placed in a deposition chamber whose interior can be kept under reduced pressure. is introduced into the deposition chamber to generate a glow discharge in the deposition chamber to form a layer consisting of Non-BN (H,X). The raw material gas for supplying B includes B ₂ H ₆ ,
Examples include compounds in a gaseous state or which can be gasified, such as B ₄ H ₁₀ B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₂ , BF ₃ and BCl ₃ . In addition, as the raw material gas for supplying N,
_N2 , _NH3 , _NF3 , _NF2Cl , _NFCl2 , _NCl3 ,
Examples include compounds in a gaseous state or capable of being gasified, such as N ₂ F ₂ , N ₂ F ₄ , NH ₂ Cl, NHF ₂ and NH ₂ F. In addition, in order to form a Non-BN (H, The BN target is sputtered by introducing it into the deposition chamber together with an inert gas such as BN to form a plasma atmosphere, or by using the B target as the target.
It is formed by introducing a large amount of the raw material gas for supplying N to form a plasma atmosphere, and sputtering it with the B target. In addition, by glow discharge method, a-Si(H,X)
In order to form a layer composed of , basically, in addition to a raw material gas for supplying Si that can supply silicon atoms (Si), a gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) is required. A source gas of 100% is introduced into a deposition chamber whose interior can be made under reduced pressure to generate a glow discharge in the deposition chamber, and is deposited on the surface of a predetermined support material made of a-Si(H, form a layer. The gas for supplying Si includes SiH ₄ , Si ₂ H ₆ ,
Silicon hydrides (silanes) in a gaseous state or that can be gasified, such as Si ₃ H ₈ and Si ₄ H ₁₀ , are mentioned, and in particular, from the viewpoint of ease of layer formation work, good Si supply efficiency, etc.
SiH ₄ and Si ₂ H ₆ are preferred. Further, the raw material gas for introducing halogen atoms includes many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen compounds in a gaseous state such as halogen-substituted silane derivatives, or halogen compounds that can be gasified. is preferred. Specifically, halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ ,
Interhalogen compounds such as IF ₇ , ICl, IBr, and
Examples include silicon halogens such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ and SiBr ₄ . When using a gaseous silicon halide or one that can be gasified as described above,
This is particularly effective because a layer composed of a-Si containing halogen atoms can be formed without separately using a raw material gas for supplying Si. In addition, the raw material gas for supplying hydrogen atoms includes hydrogen gas, halides such as HF, HCl, HBr, and HI, and silicon hydrides such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ . , or SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ ,
Gaseous or gasifiable materials such as halogen-substituted silicon hydrides such as SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , etc. can be used, and when these raw material gases are used, electric or photoelectric This is effective because the content of hydrogen atoms (H), which is extremely effective in controlling properties, can be easily controlled. When the hydrogen halide or the halogen-substituted silicon hydride is used, hydrogen atoms (H) are also introduced at the same time as the halogen atoms, which is particularly effective. In order to form a layer consisting of a-Si(H, A silicon compound gas containing halogen atoms may be introduced into the deposition chamber to form a plasma atmosphere of the gas. Further, when introducing hydrogen atoms, a raw material gas for introducing hydrogen atoms, such as H ₂ or the above-mentioned silane gases, is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Bye. For example, in the case of the reactive sputtering method, Si
Using a target, a gas for introducing halogen atoms and H ₂ gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the Si target is sputtered. A layer consisting of a-Si(H,X) is formed on the support. To form a layer composed of a-SiGe (H,X) by the glow discharge method, silicon atoms (Si)
A raw material gas for Si supply that can supply Si, a raw material gas for Ge supply that can supply germanium atoms (Ge), and a hydrogen atom (H) that can supply hydrogen atoms (H) and/or halogen atoms (X). ) or/and a raw material gas for supplying halogen atoms (X) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, a glow discharge is generated in the deposition chamber, and the source gas is placed in a predetermined position in advance. A layer composed of a-SiGe(H,X) is formed on the surface of a certain predetermined support. Substances that can be used as raw material gas for supplying Si, raw material gas for supplying halogen atoms, and raw material gas for supplying hydrogen atoms are used when forming the layer composed of a-Si(H,X) mentioned above. What you have is used as is. In addition, the substances that can be the raw material gas for supplying Ge include GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ ,
Gaseous or gasifiable germanium hydrides such as Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H ₂₀ can be used. In particular, from the viewpoint of ease of handling during layer creation work and good Ge supply efficiency,
GeH ₄ , Ge ₂ H ₆ and Ge ₃ H ₈ are preferred. a-SiGe(H,X) by sputtering method
In order to form a layer composed of , a target made of silicon and a target made of germanium are used, or a target made of silicon and germanium is used, and these are sputtered in a desired gas atmosphere. It is done by a-SiGe using ion plating method
When forming a layer composed of (H,X),
For example, polycrystalline silicon or single-crystal silicon and polycrystalline germanium or single-crystal germanium are housed in a deposition boat as evaporation sources, and the evaporation sources are heated and evaporated using a resistance heating method or an electron beam method (EB method). This can be accomplished by causing the flying evaporated material to pass through a desired gas plasma atmosphere. In both the sputtering method and the ion plating method, in order to contain halogen atoms in the layer to be formed, a gas of the above-mentioned halide or a silicon compound containing halogen atoms is introduced into the deposition chamber, and the gas is It is sufficient to form a plasma atmosphere of In addition, when introducing hydrogen atoms, a raw material gas for supplying hydrogen atoms, such as H ₂ or the above-mentioned gases such as hydrogenated silanes and/or hydrogenated germanium, is introduced into the deposition chamber for sputtering. A plasma atmosphere of gases such as the like may be formed. Further, as the raw material gas for supplying halogen atoms, the above-mentioned halides or silicon compounds containing halogen are effective, but hydrogen halides such as HF, HCl, HBr, and HI, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
Halogen-substituted silicon hydrides such as SiH ₂ Br ₂ and 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 ,
Hydrogenated germanium halides such as GeH ₃ Br, GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I, etc., GeF ₄ , GeCl ₄ ,
Gaseous or gasifiable substances such as germanium halides such as GeBr ₄ , GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ and the like can also be used as effective starting materials. Amorphous silicon containing tin atoms (hereinafter referred to as "a-SiSn (H,
X)”. ) To form a photoreceptive layer composed of a-SiGe (H, This is accomplished by using the starting material in place of the original starting material and incorporating it in a controlled amount into the layer being formed. Substances that can serve as raw material gas for supplying tin atoms (Sn) include tin hydride (SnH ₄ ) and
SnF ₂ , SnF ₄ , SnCl ₂ , SnCl ₄ , SnBr ₂ , SnBr ₄ ,
Gaseous or gasifiable tin halides such as SnI ₂ and SnI ₄ can be used. When using tin halides, a-Si containing halogen atoms can be used on a predetermined support. This is particularly effective since it is possible to form layers consisting of Among these, SnCl ₄ is preferred from the viewpoint of ease of handling during layer forming work, good Sn supply efficiency, and the like. When SnCl ₄ is used as a starting material for supplying tin atoms (Sn), to gasify it,
It is desirable to heat solid SnCl ₄ and to bubble it with an inert gas such as Ar or He.The gas thus generated is then deposited into the desired deposition chamber with a reduced pressure inside. Introduce under gas pressure. a-Si(H,X) using glow discharge method, sputtering method, or ion plating method
In order to form a layer composed of an amorphous material containing a group atom or a group atom, nitrogen atom, oxygen atom or carbon atom, a-Si(H,X)
When forming the layer, a starting material for introducing a group atom or a starting material for introducing a group atom, a starting material for introducing an oxygen atom, a starting material for introducing a nitrogen atom, or a starting material for introducing a carbon atom is used. -Si (H, For example, using the glow discharge method, atoms (O,
To form a layer composed of a-Si(H,X) containing C, N), atoms (O ,C,
N) by using the starting materials for the introduction together with the starting materials for forming a-Si(H,X) and incorporating them in controlled amounts into the formed layer. As a starting material for such introduction of atoms (O, C, N), almost any gaseous substance or substance that can be gasified contains at least atoms (O, C, N). Can be used. Specifically, starting materials for introducing oxygen atoms (O) include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), nitrogen monooxide (N ₂ O), and nitrogen sesquioxide ( N ₂ O ₃ ), nitrogen tetroxide (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 lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ), and examples of starting materials for introducing carbon atoms (C) include, for example, , methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (n-
Saturated hydrocarbons having 1 to 5 carbon atoms such as C ₄ H ₁₀ ), pentane (C ₅ H 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., ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and other acetylenic hydrocarbons having 2 to 4 carbon atoms, and examples of starting materials for introducing nitrogen atoms (N) include nitrogen (N ₂ ),
Ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ),
Examples include hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen trifluoride (F ₃ N), and nitrogen tetrafluoride (F ₄ N). For example, when a glow discharge method is used to form a layer or layer region containing oxygen atoms, oxygen atoms are introduced into the starting materials selected from the above-mentioned starting materials for forming the light-receiving member layer. The starting materials for are added. As such a starting material for introducing oxygen atoms, almost any gaseous substance or substance that can be gasified can be used as long as it has at least an oxygen atom as a constituent atom. For example, a source gas containing silicon atoms (Si), a source gas containing oxygen atoms (O), and hydrogen atoms (P) and/or halogen atoms (X) as necessary. A raw material gas containing silicon atoms (Si) and oxygen atoms (O) can be used by mixing them at a desired mixing ratio.
and a raw material gas containing hydrogen atoms (H) as constituent atoms,
This is also mixed at a desired mixing ratio, or with a raw material gas containing silicon atoms (Si) as constituent atoms,
A raw material gas having three constituent atoms: silicon atom (Si), oxygen atom (O), and hydrogen atom (H) can be used in combination. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
A raw material gas containing oxygen atoms (O) as constituent atoms may be mixed with a raw material gas containing oxygen atoms (O) as constituent atoms. 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) and oxygen atoms (O)
For example, lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ) having a hydrogen atom (H) and a hydrogen atom (H) as constituent atoms can be mentioned. To form a layer or layer region containing oxygen atoms by sputtering, single crystal or Si
This can be carried out by sputtering a wafer, a SiO ₂ wafer, or a wafer containing a mixture of Si and SiO ₂ in various gas atmospheres. For example, if a Si wafer is used as a target, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as required, and then placed in a sputtering deposition chamber. The Si wafer may be sputtered by introducing these gases and forming a gas plasma of these gases. Alternatively, by using Si and SiO ₂ as separate targets or using a single mixed target of Si and SiO ₂ , it is possible to use a diluted gas atmosphere for sputtering or at least hydrogen. It can be formed by sputtering in a gas atmosphere containing atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms in the raw material gas shown in the glow discharge example mentioned above is
It can also be used as an effective gas in sputtering. For example, in order to form a layer composed of amorphous silicon containing carbon atoms by the glow discharge method, a raw material gas containing silicon atoms (Si) and carbon atoms (C) as constituent atoms is used. Raw material gas and, if necessary, hydrogen atoms (H) or/
and a raw material gas whose constituent atoms are halogen atoms (X) at a desired mixing ratio, or a raw material gas whose constituent atoms are silicon atoms (Si) and carbon atoms (C) and hydrogen atoms. (H) is also mixed with a raw material gas at a desired mixing ratio, or silicon atoms (Si) are used.
A raw material gas containing as constituent atoms and a raw material gas containing silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H) as constituent atoms, or furthermore, a raw material gas containing silicon atoms and hydrogen atoms as constituent atoms. Use a mixture of raw material gases. The gases effectively used as such raw material gases are SiH ₄ , Si ₂ H ₆ , and
Silicon hydride gas such as silanes such as Si ₃ H ₈ Si ₄ H ₁₀ , saturated hydrocarbons containing C and H as constituent atoms, e.g. having 1 to 4 carbon atoms, ethylene having 2 to 4 carbon atoms Examples include hydrocarbons, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like. Specifically, examples of saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (n-C ₄ H ₁₀ ), and pentane (C ₅ H ₁₂ ), ethylene hydrocarbons include ethylene (C ₂ H ₆ ), 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 ). Examples of acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene ( C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like. Examples of the source gas containing Si, C, and H as constituent atoms include alkyl silicides such as Si(CH ₃ ) ₄ and Si(C ₂ H ₅ ) ₄ . In addition to these raw material gases, H
Of course, H ₂ can also be used as the raw material gas for introduction. a-SiC(H,X) by sputtering method
To form a layer composed of a single crystal or polycrystalline Si wafer or a C (graphite) wafer,
Alternatively, sputtering may be performed using a wafer containing a mixture of Si and C as a target in a desired gas atmosphere. For example, when using a Si wafer as a target, the raw material gas for introducing carbon atoms, hydrogen atoms, and/or halogen atoms is diluted with a diluent gas such as Ar or He as necessary, and sputtering is performed. The Si wafer may be sputtered by introducing such a gas into a deposition chamber to form a gas plasma of these gases. In addition, if Si and C are used as separate targets, or if Si and C are used as a mixed target, the sputtering gas may be used as a raw material for introducing hydrogen atoms and/or halogen atoms. The gas may be diluted with a diluent gas as necessary and introduced into a deposition chamber for sputtering to form a gas plasma and perform sputtering.
As the raw material gas for introducing each atom used in the sputtering method, the raw material gas used in the glow discharge method described above can be used as is. For example, when a glow discharge method is used to form a layer or layer region containing nitrogen atoms, nitrogen atoms can be introduced into the starting materials selected from the above-mentioned starting materials for forming the photoreceptive layer. Add starting material. As the starting material for introducing nitrogen atoms, almost any gaseous substance or gasifiable substance having at least nitrogen atoms as a constituent atom can be used. For example, a source gas containing silicon atoms (Si), a source gas containing nitrogen atoms (N), and hydrogen atoms (H) and/or halogen atoms (X) as necessary. A raw material gas containing silicon atoms (Si) and nitrogen atoms (N) can be used by mixing them at a desired mixing ratio.
Also, hydrogen atoms (H) can be used by mixing the constituent atoms and the raw material gas at a desired mixing ratio. Also, separately, silicon atoms (Si) and hydrogen atoms (H)
A raw material gas containing nitrogen atoms (N) as constituent atoms may be mixed with a raw material gas containing nitrogen atoms (N) as constituent atoms. A starting material that is effectively used as a raw material gas for introducing nitrogen element (N) used when forming a layer or layer region containing nitrogen atoms has N as a constituent atom or has N and H as a constituent atom. Gaseous or gasifiable nitrogen such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ) as atoms; , boron nitrides, azides, and other nitrogen compounds. In addition, halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N) can be used because they can introduce halogen atoms in addition to nitrogen atoms. Can be mentioned. To form a layer or layer region containing nitrogen atoms by sputtering, single crystal or Si
By sputtering wafers, polycrystalline Si wafers, Si ₃ N ₄ wafers, or wafers containing a mixture of Si (Si ₃ N ₄₎ in various gas atmospheres. Just go with it. For example, if a Si wafer is used as a target, the raw material gas for introducing nitrogen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as required, and the sputtering is carried out in a deposition chamber for sputtering. The Si wafer may be sputtered by introducing these gases into a gas plasma and forming a gas plasma of these gases. Alternatively, Si and Si ₃ N ₄ can be used as separate targets, or by using a mixed target of Si and Si ₃ N ₄ in a diluent gas atmosphere as a sputtering gas. or by sputtering in a gas atmosphere containing at least hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing nitrogen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering. In addition, when forming a layer composed of group atoms or a-Si(H,X) containing group atoms using a glow discharge method, sputtering method, or ion plating method, or by using the starting materials for the introduction of group atoms together with the starting materials for forming a-Si(H, Let's do it. Specifically, starting materials for introducing group atoms include B ₂ H ₆ , B ₄ H ₁₀ ,
Examples include boron hydrides such as B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ and B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga
(CH ₃ ) ₂ , InCl ₃ , TlCl ₃ and the like may also be mentioned. For introducing group atoms and as a starting material, specifically for introducing phosphorus atoms, hydrogenated phosphorus such as PH ₃ and P ₂ H ₆ is used.
_PH4I , _PF3 , _PF5 , _PCl3 , _PCl5 , _PBr3 , _PBr5 ,
Examples include halogenated phosphorus such as PI ₃ . In addition,
_AsH3 , _AsF3 , _AsCl3 , _AsBr3 , _AsF5 , _SbH3 ,
_SbF3 , _SbF5 , _SbCl3 , _SbCl5 , _BiH3 , _BiCl3 ,
BiBr ₅ and the like can also be mentioned as effective starting materials for the introduction of group atoms. As described above, the light-receiving layer of the light-receiving member of the present invention is formed using a glow discharge method, a sputtering method, or the like. Controlling the content of each group atom, oxygen atom, carbon atom or nitrogen atom, or hydrogen atom or/and halogen atom flowing into the deposition chamber,
This is carried out by controlling the gas flow rate of each starting material for supplying atoms or the gas flow rate ratio between the starting materials for supplying atoms. In addition, conditions such as support temperature, gas in the deposition chamber, and discharge power during formation of each constituent layer such as the photoconductive layer and surface protective layer are important factors in obtaining a light-receiving member with desired characteristics. It is selected as appropriate, taking into consideration the function of the layer to be formed.
Furthermore, these layer formation conditions may differ depending on the type and amount of each of the atoms mentioned above to be contained in each constituent layer such as the photoconductive layer and the surface protective layer. It is also necessary to take into consideration the quantity, etc. when making a decision. Specifically, when forming a surface protective layer made of Non-BN (N, is usually 10 ^-2 ~
10 Torr, more preferably 5×10 ² ~
2 Torr, optimally 0.1 to 1 Torr. In addition, the support temperature is usually 50 to 700°C, but especially for non-
50 to 400℃, poly
- When forming the BN(H,X) layer, the temperature is 200 to 700°C. Further, the discharge power is usually 0.01 to 5 W/cm ² , more preferably 0.02 to 2 W/cm ² . Furthermore,
The gas flow ratio of the B supply raw material gas, the N supply raw material gas, and the Ar gas is such that B/N is 1/100 to 5/1,
More preferably, it is 1/80 to 4/1,
Ar/B+N should be 1/1 to 0. In addition, a 4-coordinate structure and a 3-coordinate structure were mixed.
When forming a surface protective layer ^made of Non-BN (H,
More preferably 5×10 ^-4 ~1.0Torr, optimally 5
×10 ^-4 ~0.7Torr, discharge power is usually 0.1~
50 W/cm ² , more preferably 0.2 to 30 W/cm ² .
The support temperature and the gas flow rate ratio of each source gas are the same as in the case of the high frequency plasma CVD method described above. Furthermore, a four-coordinate structure and a three-coordinate structure were mixed.
When forming ^a surface protective layer made of Non-BN (H,
10 ^-4 ~0.7Torr, discharge power is 0.01 ~
10 W/cm ² , more preferably 0.05 to 8 W/cm ² .
The support temperature is the same as in the case of the high frequency plasma CVD method described above. In addition, when forming a layer made of a-Si (H,
-350°C, particularly preferably 50-250°C. The gas pressure in the deposition chamber is usually 0.01 to 1 Torr, particularly preferably 0.1 to 0.5 Torr. The discharge power is usually 0.005 to 50W/ ^cm2 ,
More preferably 0.01 to 30 W/cm ² 5. Particularly preferably, it is 0.01 to 20 W/cm ² . When forming an a-SiGe (H, Temperature, usually 50~
The temperature is 350°C, more preferably 50 to 300°C, particularly preferably 100 to 300°C. The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.001 to 3 Torr, particularly preferably 0.01 Torr.
~1 Torr. In addition, the discharge power is 0.005 ~
Normally it is 50W/ ^cm2 , but preferably
0.01~30W/ ^cm2 . Particularly preferably 0.01~
20W/ ^cm2 . However, the specific conditions for layer formation, such as support temperature, discharge power, and gas pressure in the deposition chamber, are usually difficult to determine individually. Therefore, in order to form an amorphous material layer with desired characteristics, it is desirable to determine optimal conditions for layer formation based on mutual and organic relationships. Next, a method for manufacturing a light receiving member formed by a glow discharge decomposition method will be described. FIG. 2 shows an apparatus for producing electrophotographic light-receiving members using the glow discharge decomposition method. 202, 203, 204, 205, 20 in the diagram
The raw material gas for forming each layer of the present invention is sealed in the gas cylinder 6, and as an example, 202 is SiH ₄ gas (purity
99.999%) cylinder, 203 diluted with _H2
B ₂ H ₆ gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ /H ₂ ) cylinder, 204 is NO gas (purity 99.5%) cylinder, 205 is B ₂ H ₆ gas diluted with He (purity
99.999%, hereinafter abbreviated as B ₂ H ₆ /He) cylinder, 20
6 is a NH ₃ gas (purity 99.999%) cylinder. To allow these gases to flow into the reaction chamber 201, make sure that the valves of the gas cylinders 202 to 206 and the leak valve 235 are closed, and also close the inflow valves 212 to 216 and the outflow valves 217 to 2.
21. After confirming that the auxiliary valves 232 to 233 are open, first open the main valve 234 to exhaust the reaction chamber 201 and gas piping. Next, when the reading on the vacuum gauge 236 reaches approximately 5×10 ^-6 Torr, the auxiliary valves 232 to 233 and the outflow valve 21
Close 7-221. To give an example of forming the first layer on the base cylinder 237, from the gas cylinder 202
SiH ₄ gas, gas cylinder, B ₂ H ₆ /H ₂ gas, gas cylinder from 203, NO gas from 204, valve 2
22, 223, 224 and outlet pressure gauge 22
7,228,229 to 1Kg/cm ² and gradually open the inflow valves 212,213,214, the mass flow controllers 207,208,20
9. Subsequently, the outflow valve 217,
218, 219, the auxiliary valve 232 is gradually opened to allow gas to flow into each reaction chamber. At this time
The outflow valve 21 is adjusted so that the ratio of SiH ₄ gas flow rate, B ₂ H ₆ /H ₂ gas flow rate, and NO gas flow rate becomes the desired value.
7, 218, and 219, and also adjust the opening of the main valve 234 while checking the reading on the vacuum gauge 236 so that the pressure in the reaction chamber reaches the desired value. Then, the temperature of the base cylinder 237 becomes higher than that of the heating heater 2.
After confirming that the temperature is set at 50 to 350°C by step 38, the power supply 240 is set to the desired power to generate glow discharge in the reaction chamber 201 and form the first layer on the base cylinder. do. When the first layer contains halogen atoms, for example, SiF ₄ gas is further added to the above gas and the mixture is sent into the reaction chamber 201 . Depending on the selection of gas species when forming each layer, the layer formation speed can be further increased. for example
If layer formation is performed using Si ₂ H ₆ gas instead of SiH ₄ gas, the productivity can be increased several times, improving productivity. To form a second layer on the first layer created as described above, the outflow valves 217 to 221 are closed, the auxiliary valves 232 to 233 are opened, and the main valve 234 is fully opened to drain the system. Once evacuated to a high vacuum, B ₂ H ₆ /H ₂ gas and NH ₃ gas are flowed into the reaction chamber 202 at the desired flow rate ratio by the same valve operation as in the case of forming the first layer. This is accomplished by generating a glow discharge according to the following conditions. When changing the amount of hydrogen atoms contained in the second layer, for example, H ₂ gas is added to the above gas and the flow rate of H ₂ gas introduced into the reaction chamber 101 is adjusted as desired. It can be controlled as desired by arbitrarily changing the value. When the second layer contains halogen atoms, for example, NF ₃ gas is further added to the above gas and the mixture is fed into the reaction chamber 201 . Needless to say, when forming each layer, all outflows other than the gases necessary are closed. Also, when forming each layer, the gas used to form the previous layer is inside the reaction chamber 201, and the outflow valves 217 to 217 are closed. 221 to the inside of the reaction chamber 201, the outflow valves 217 to 221 are closed, the auxiliary valves 232 to 233 are opened, and the main valve 23
4 is fully opened and the system is once evacuated to high vacuum as necessary. Further, during layer formation, the base cylinder 237 is operated by the motor 23 in order to ensure uniform layer formation.
9 at the desired speed. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 Using the manufacturing apparatus shown in FIG. 2, an electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder according to the preparation conditions shown in Table 1. Separately, using the same type of apparatus as shown in FIG. 2, an aluminum substrate and a single crystal Si wafer were placed in a sample holder on a cylinder, and a separate sample with the same specifications on which only the surface layer was formed was prepared. For the light-receiving member (hereinafter referred to as a drum), set up an electrophotographic device and check the electrophotographic characteristics such as initial chargeability, residual potential, ghost, etc. under various conditions. We investigated the decrease in charging ability, surface scraping, increase in image defects, etc. after running on a 10,000-sheet machine.
Furthermore, the cleaner blade was intentionally replaced with one whose rubbing edge was worn out, and the cleaning performance was compared based on the degree of background fog generated on a solid white image. Furthermore, image blurring of the drum was also evaluated in a high temperature and high humidity atmosphere of 35° C. and 85%. In addition, the dielectric strength was investigated by applying a DC high voltage to the drum. Furthermore, scratch resistance was examined by applying a constant load to a needle with a spherical tip and scratching the drum surface. The above evaluation results are shown in Table 2. As seen in Table 2, good results were obtained for the main items. In particular, superiority was recognized in terms of image defects, image deletion, and cleanability (degree of background fog). When we investigated the coordination numbers of the surface layer-only films (hereinafter referred to as samples) deposited on an aluminum substrate and a single-crystal Si wafer using EXAFS and IR, we found that:
It was found that it was a mixture of 4- and 3-coordination. In addition, on the Si wafer sample for which IR measurements were completed, scratches of □/mm were made in a grid pattern with a diamond needle, and a peel test was performed using adhesive tape to determine the magnitude of residual stress. Example 2 A drum and sample were prepared in the same manner as in Example 1 under the preparation conditions shown in Table 3 by adding H ₂ gas to the raw material gas for the surface layer, and the same evaluations were performed. The results are shown in Table 4. As seen in Table 4, the same characteristics as in Example 1 were obtained. Further, as a result of measuring the sample, it was found that it was a mixture of 4-coordinate and 3-coordinate. Example 3 A drum and sample were prepared in the same manner as in Example 1 under the preparation conditions shown in Table 1, with the bias voltage of the cylinder set to +100V during the preparation of the surface layer, and the same evaluation was performed. The results are shown in Table 5. As seen in Table 5, the same characteristics as in Example 1 were obtained. Further, as a result of measuring the sample, it was found that it was a mixture of 4-coordinate and 3-coordinate. Example 4 A drum was prepared in the same manner as in Example 1 under the conditions shown in Table 6 for the charge injection blocking layer, photoconductive layer, and surface layer, and the same evaluation was performed. The results are shown in Table 7. As shown in Table 7, the same characteristics as in Example 1 were obtained. Example 5 An aluminum cylinder was anodized to create an aluminum oxide layer (Al ₂ O ₃ ) on the cylinder surface, which was used as a charge injection blocking layer, and a photoconductive layer and a surface layer were formed on this layer. Drums were produced in the same manner as in Example 1 under the production conditions shown in Table 8, and the same evaluations were performed. The results are shown in Table 9. As shown in Table 9, the same characteristics as in Example 1 were obtained. Example 6 Long wavelength light absorption layer (hereinafter referred to as "IR absorption layer"),
A drum was prepared in the same manner as in Example 1 under the conditions shown in Table 10 for the photoconductive layer and the surface layer, and the same evaluation was performed. Furthermore, the drum was set in an electrophotographic apparatus using a semiconductor laser having a wavelength of 785 nm as a light source for image exposure, and it was checked whether interference fringes appeared on the image. The results are shown in Table 11. As seen in Table 11, the same characteristics as in Example 1 were obtained, and no interference fringes appeared. Example 7 A drum was prepared in the same manner as in Example 1 under the conditions shown in Table 12 for adhesion, photoconductive layer, and surface layer, and was evaluated in the same manner. The results are shown in Table 13. As seen in Table 13, the same characteristics as in Example 1 were obtained. Example 8 A drum was prepared in the same manner as in Example 1, with the IR absorption layer, charge injection blocking layer, photoconductive layer, and surface layer each under the conditions shown in Table 14, and the same evaluation as in Example 6 was conducted. Ivy. The results are shown in Table 15. As seen in Table 15, the same characteristics as in Example 1 were obtained. Example 9 A drum was prepared in the same manner as in Example 1 under the conditions shown in Table 16 for the adhesion layer, charge injection blocking layer, photoconductive layer, and surface layer, and the same evaluation was performed. The results are shown in Table 17. As seen in Table 17, the same characteristics as in Example 1 were obtained. Example 10 A drum was prepared in the same manner as in Example 1, with the adhesion layer, IR absorption layer, charge injection blocking layer, photoconductive layer, and surface layer each under the conditions shown in Table 18.
A similar evaluation was made. The results are shown in Table 19. As seen in Table 19, the same characteristics as in Example 1 were obtained. Example 11 The conditions for forming the photoconductive layer were changed to several conditions shown in Table 20, and the other conditions were the same as in Example 1.
Prepared multiple drums. As a result of subjecting these drums to the same evaluation as in Example 1, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 1. Example 12 The conditions for forming the photoconductive layer were changed to several conditions shown in Table 21, and the other conditions were the same as in Example 2.
Prepared multiple drums. As a result of subjecting these drums to the same evaluation as in Example 2, all drums were obtained that fully satisfied the electrophotographic characteristics as in Example 2. Example 13 The conditions for forming the photoconductive layer were changed to several conditions shown in Table 22, and the other conditions were the same as in Example 3.
Prepared multiple drums. As a result of subjecting these drums to the same evaluation as in Example 3, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 3. Example 14 A plurality of drums were prepared under the same conditions as in Example 4 except that the conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 23. As a result of subjecting these drums to the same evaluation as in Example 4, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 4. Example 15 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 24, and the conditions for forming the photoconductive layer were changed to several conditions shown in Table 25, but otherwise the same as in Example 4. A plurality of drums shown in Table 26 were prepared under the following conditions. As a result of subjecting these drums to the same evaluation as in Example 4, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 4. Example 16 The conditions for forming the charge injection blocking layer were changed to the conditions shown in Table 24, the conditions for forming the photoconductive layer were changed to the conditions shown in Table 27, and the conditions for forming the surface layer were changed to the conditions shown in Table 28. A plurality of drums shown in Table 29 were prepared under the conditions shown in the table. As a result of subjecting these drums to the same evaluation as in Example 4, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 4. Example 17 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 24, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for forming the surface layer were changed to conditions shown in Table 30. A plurality of drums shown in Table 31 were prepared under the conditions shown in the table. As a result of subjecting these drums to the same evaluation as in Example 4, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 4. Example 18 The conditions for forming the photoconductive layer were changed to several conditions shown in Table 25, and the other conditions were the same as in Example 5.
A plurality of drums shown in Table 32 were prepared. As a result of subjecting these drums to the same evaluation as in Example 5, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 5. Example 19 The conditions for creating the surface layer were changed to those shown in Table 28,
The conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the other conditions were the same as in Example 5.
33 Several drums shown in Table 3 were prepared. As a result of subjecting these drums to the same evaluation as in Example 5, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 5. Example 20 The conditions for creating the surface layer were changed to those shown in Table 30,
The conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the other conditions were the same as in Example 5.
34 Several drums shown in Table 3 were prepared. As a result of subjecting these drums to the same evaluation as in Example 5, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 5. Example 21 A plurality of drums shown in Table 37 were prepared under the same conditions as in Example 6 except that the conditions for creating the IR absorption layer were changed to several conditions shown in Tables 35 and 36. As a result of subjecting these drums to the same evaluation as in Example 6, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 6. Example 22 The conditions for forming the IR absorbing layer were changed to several conditions shown in Tables 35 and 38, and the conditions for forming the photoconductive layer were changed to several conditions shown in Table 25, except for the same conditions as in Example 6. A plurality of drums shown in Table 39 were prepared under similar conditions. As a result of subjecting these drums to the same evaluation as in Example 6, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 6. Example 22 The conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 38, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for forming the surface layer were changed to several conditions shown in Table 27. A plurality of drums shown in Table 40 were prepared under the conditions shown in Table 28. As a result of subjecting these drums to the same evaluation as in Example 6, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 6. Example 24 The conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 38, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for forming the surface layer were changed to several conditions shown in Table 27. A plurality of drums shown in Table 41 were prepared under the conditions shown in Table 30. As a result of subjecting these drums to the same evaluation as in Example 6, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 6. Example 25 The conditions for forming the adhesive layer were changed to several conditions shown in Table 42, and the other conditions were the same as in Example 7.
43 Several drums shown in Table 4 were prepared. These drums were subjected to the same evaluation as in Example 7, and as in Example 7, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 26 The conditions for forming the adhesive layer were changed to several conditions shown in Table 44, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 25, and the other conditions were the same as in Example 7. A plurality of drums shown in Table 45 were prepared. These drums were subjected to the same evaluation as in Example 7, and as in Example 7, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 27 The conditions for forming the adhesive layer were changed to several conditions shown in Table 44, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for forming the photoconductive layer were changed to several conditions shown in Table 46. I prepared a drum. These drums were subjected to the same evaluation as in Example 7, and as in Example 7, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 28 The conditions for forming the adhesive layer were changed to the conditions shown in Table 44, the conditions for forming the photoconductive layer were changed to the conditions shown in Table 27, and the conditions for forming the surface layer were changed to the conditions shown in Table 30. A plurality of drums shown in Table 47 were prepared under the conditions shown. These drums were subjected to the same evaluation as in Example 7, and as in Example 7, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 29 A plurality of drums shown in Table 48 were prepared under the same conditions as in Example 8 except that the conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 36. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 30 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 49, and the conditions for forming the IR absorption layer were changed to those shown in Table 49.
Example 8 with several conditions shown in the table.
A plurality of drums shown in Table 50 were prepared under the same conditions as above. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 31 The conditions for creating the charge injection blocking layer were changed to several conditions shown in Table 51, and the conditions for creating the IR absorption layer were changed to those shown in Table 35 and 38.
A plurality of drums shown in Table 52 were prepared under the conditions shown in Table 52, with the surface layer forming conditions shown in Table 28, by changing the conditions shown in the table. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 32 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, and the conditions for forming the IR absorption layer were changed to those shown in Table 35 and 38.
A plurality of drums shown in Table 53 were prepared under the conditions shown in Table 30 for forming the surface layer by changing the conditions shown in the table. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 33 A plurality of drums shown in Table 55 were prepared under the same conditions as in Example 9 except that the conditions for forming the adhesive layer were changed to several conditions shown in Tables 44 and 54. As a result of subjecting these drums to the same evaluation as in Example 9, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 9. Example 34 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 56, the conditions for forming the adhesive layer were changed to several conditions shown in Tables 44 and 57, and the other conditions were the same as in Example 9. A plurality of drums shown in Table 58 were prepared under similar conditions. As a result of subjecting these drums to the same evaluation as in Example 9, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 9. Example 35 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 24, the conditions for forming the adhesive layer were changed to several conditions shown in Tables 44 and 57, and the conditions for forming the surface layer were changed to several conditions shown in Tables 44 and 57. 28
A plurality of drums shown in Table 59 were prepared under the conditions shown in the table. As a result of subjecting these drums to the same evaluation as in Example 9, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 9. Example 36 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 24, the conditions for forming the adhesive layer were changed to several conditions shown in Tables 44 and 57, and the conditions for forming the surface layer were changed to several conditions shown in Tables 44 and 57. 30
A plurality of drums shown in Table 60 were prepared under the conditions shown in the table. As a result of subjecting these drums to the same evaluation as in Example 9, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 9. Example 37 A plurality of drums shown in Table 62 were prepared under the same conditions as in Example 10 except that the conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 61. These drums were subjected to the same evaluation as in Example 10, and as in Example 10, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 38 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 64, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 63, and the other conditions were the same as in Example 10. A plurality of drums shown in Table 65 were prepared under similar conditions. These drums were subjected to the same evaluation as in Example 10, and as in Example 10, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 39 The conditions for forming the charge injection blocking layer were changed to the conditions shown in Table 64, the conditions for forming the photoconductive layer were changed to the conditions shown in Table 66, and the conditions for forming the surface layer were changed to the conditions shown in Table 28. A plurality of drums shown in Table 67 were prepared under the conditions shown in the table. These drums were subjected to the same evaluation as in Example 10, and as in Example 10, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 40 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 64, the conditions for forming the photoconductive layer were changed to several conditions shown in Table 66, and the conditions for forming the surface layer were changed to several conditions shown in Table 64. A plurality of drums shown in Table 68 were prepared under the conditions shown in the table. These drums were subjected to the same evaluation as in Example 10, and as in Example 10, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 41 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, and the conditions for forming the IR absorption layer were changed to those shown in Table 35 and 38.
By changing the conditions shown in the table, changing the conditions for forming the photoconductive layer to the conditions shown in Table 69, and changing the conditions for forming the surface layer to the conditions shown in Table 70, a plurality of drums shown in Table 71 were prepared. Prepared. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 42 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, and the conditions for forming the IR absorption layer were changed to those shown in Table 35 and 38.
By changing the several conditions shown in the table, changing the conditions for forming the photoconductive layer to the conditions shown in Table 72, and changing the conditions for forming the surface layer to the conditions shown in Table 70, a plurality of drums shown in Table 73 were used. Prepared. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 43 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, and the conditions for forming the IR absorption layer were changed to those shown in Table 35 and 38.
By changing the several conditions shown in the table, changing the conditions for forming the photoconductive layer to the conditions shown in Table 69, changing the conditions for forming the surface layer to the conditions shown in Table 28, and forming a plurality of drums shown in Table 74. Prepared. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 44 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, and the conditions for forming the IR absorption layer were changed to those shown in Table 35 and 38.
By changing the conditions shown in the table, changing the conditions for forming the photoconductive layer to the conditions shown in Table 72, and changing the conditions for forming the surface layer to the conditions shown in Table 28, a plurality of drums shown in Table 75 were used. Prepared. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 45 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, and the conditions for forming the IR absorption layer were changed to those shown in Table 35 and 38.
By changing the conditions shown in the table, changing the conditions for forming the photoconductive layer to the conditions shown in Table 69, changing the conditions for forming the surface layer to the conditions shown in Table 30, and forming a plurality of drums shown in Table 76. Prepared. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 46 The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, and the conditions for forming the IR absorption layer were changed to those shown in Table 35 and 38.
By changing the conditions shown in the table, changing the photoconductive layer formation conditions to the conditions shown in Table 72, and changing the surface layer formation conditions to the conditions shown in Table 30, a plurality of drums shown in Table 77 were prepared. Prepared. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 47 A plurality of drums were prepared under conditions for forming a charge injection blocking layer and a photoconductive layer as shown in Table 78, and under conditions for forming a surface layer as shown in Table 79. As a result of subjecting these drums to the same evaluation as in Example 4, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 4. Example 48 A plurality of drums were prepared under conditions for forming an IR absorbing layer, a charge injection blocking layer, and a photoconductive layer as shown in Table 80, and for forming a surface layer as shown in Table 81. These drums were subjected to the same evaluation as in Example 8, and as in Example 8, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 49 A plurality of drums were prepared under conditions for forming an adhesion layer, IR absorption layer, charge injection blocking layer, and photoconductive layer as shown in Table 82, and conditions for forming a surface layer as shown in Table 83. These drums were subjected to the same evaluation as in Example 10, and as in Example 10, all drums were obtained that fully satisfied the electrophotographic characteristics. Example 50 A drum was prepared in the same manner as in Example 1, with the charge injection blocking layer, photoconductive layer, intermediate layer, and surface layer prepared under the conditions shown in Table 84, and the same evaluation was conducted.
As in Example 1, a drum with extremely excellent electrophotographic properties was obtained. Example 51 The mirror-finished cylinder was further subjected to lathe processing using a sword tool with various angles, and a plurality of cylinders with the determined shape as shown in Figure 3 and various cross-sectional patterns as shown in Table 85 were prepared. did. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 2 and subjected to drum manufacturing under the same manufacturing conditions as in Example 1. The produced drums were evaluated in the same manner as in Example 1, and as a result, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 1. Example 52 The surface of the mirror-finished cylinder was subjected to a so-called surface dimple treatment, in which the surface of the cylinder was exposed to the falling of many bearing balls, resulting in countless dents on the cylinder surface, as shown in Fig. 4. A plurality of cylinders with various cross-sectional patterns as shown in Table 86 were prepared. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 2 and subjected to drum manufacturing under the same manufacturing conditions as in Example 1. The produced drums were evaluated in the same manner as in Example 1, and as a result, all drums were obtained which fully satisfied the electrophotographic characteristics as in Example 1.

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[Summary of effects of the invention]

The light-receiving member of the present invention has particularly excellent properties due to the provision of a surface protective layer made of a non-single crystal material containing a mixture of boron nitride having a four-coordinate structure and boron nitride having a three-coordinate structure. The light-receiving member of the present invention has excellent moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, etc., and when the light receiving member of the present invention is applied as an electrophotographic image forming member, the residual potential is low. The electrical characteristics are stable, and the image defects, image deletion, and cleaning properties are particularly excellent.

[Brief explanation of drawings]

Figures 1A to I are diagrams schematically showing some typical examples of layered structures of the light-receiving member of the present invention, and Figure 2 is an example of an apparatus for manufacturing the light-receiving member of the present invention. , is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method. FIGS. 3 and 4 are diagrams showing examples of the cross-sectional shape of the support of the light-receiving member of the present invention. 100... Light receiving member, 101... Support, 1
02...Photoconductive layer, 103...Surface protection layer, 10
4...Charge injection blocking layer, 105...Long wavelength light absorption layer, 106...Adhesion layer, 107...Free surface, 1
08...Intermediate layer, 201...Reaction chamber, 202-2
06... Gas cylinder, 207-211... Mass flon controller, 212-216... Inflow valve, 217-221... Outflow valve, 222-2
26... Valve, 227-231... Pressure regulator, 232, 233... Auxiliary valve, 234...
Main valve, 235...Leak valve, 236
... Vacuum gauge, 237 ... Base cylinder, 238
... Heater, 239 ... Motor, 240
...High frequency power supply.

Claims (1)

[Scope of Claims] 1. A support, a photoconductive layer formed on the support of an amorphous material having silicon atoms as a matrix and containing at least one of hydrogen atoms or halogen atoms, and a surface of the photoconductive layer. In the light-receiving member, the surface protection layer includes a polycrystalline material containing a mixture of boron nitride having a four-coordination structure and boron nitride having a three-coordination structure. A light receiving member comprising a non-single crystal material. 2. The light-receiving member according to claim 1, wherein the light-receiving layer has a multilayer structure of three or more layers. 3. The light-receiving member according to claim 1, wherein the light-receiving layer has a charge injection blocking layer. 4. The light receiving member according to claim 2, wherein the light receiving layer has a long wavelength light absorption layer. 5. The light-receiving member according to claim 2, wherein the light-receiving layer has an adhesive layer having a function of improving adhesiveness. 6. The light-receiving member according to claim 2, further comprising an intermediate layer between the photoconductive layer and the surface protection layer.