JPH0746234B2 - Light receiving member - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a light-receiving member having a photoconductive layer composed of amorphous silicon having silicon atoms as a matrix, and particularly to a surface protective layer having excellent properties. The present invention relates to a light receiving member provided on a photoconductive layer and suitable for an electrophotographic photoreceptor.

[Description of Prior Art]

Conventionally, as a light-receiving member used for an electrophotographic photoreceptor or the like, in addition to excellent matching in the light-sensitive region as compared with other types of light-receiving members, it also has a high Pickers hardness and is free from pollution. From the viewpoint of few problems, for example, JP-A-54-8
Amorphous materials containing silicon atoms as a matrix and containing at least one of hydrogen atoms and / or halogen atoms (hereinafter referred to as "a-Si (H, X)" as disclosed in 6341 and JP-A-56-83746. ) ”) The light receiving member is drawing attention.

By the way, such a light receiving member is formed on the support by a-Si.
A photoconductive layer composed of (H, X) prevents the injection of charges from the free surface side into the photoconductive layer when the photoconductive layer is subjected to a charging treatment. ,
A surface protective layer is provided on the photoconductive layer in order to improve moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, etc. of the photoconductive layer and obtain stable image quality for a long period of time. It is known to provide.

And, regarding the surface protective layer, where it is required to efficiently exhibit the various functions described above, various non-single crystalline materials having high resistance and sufficient light transmittance, that is, amorphous materials or / And polycrystalline materials have been proposed, and as one of those proposals, an amorphous material containing boron nitride (hereinafter referred to as "a-BN").
It is known to use a thin film composed of (See JP-A-59-12448 and JP-A-60-61760) However, when a thin film composed of the a-BN is used as a surface protective layer, sometimes the a-BN thin film is charged. Deterioration occurs due to various mechanical damages such as corona discharge in the treatment and contact with other members such as a cleaning blade, and exerts the above-mentioned various functions required for the surface protective layer for a long period of time. There is a problem that it becomes impossible. Further, the light receiving member using the a-BN thin film has insufficient chargeability, and when an image is formed using such a light receiving member, image quality is deteriorated such as ghost on the image. There is also the problem that it may appear as.

[Object of the Invention]

The present invention solves the above-mentioned problems relating to the surface protective layer in the light receiving member used for the electrophotographic photoreceptor and the like, and provides a light having an improved surface protective layer that exhibits desired functions over a long period of time. The main purpose is to provide a receiving member.

Another object of the present invention is to provide a light receiving member used for an electrophotographic photoreceptor or the like that has a stable charging ability at all times and can obtain an image of excellent quality for a long period of time.

[Structure of Invention]

The inventors of the present invention have made extensive studies to solve the above-mentioned problems relating to the surface protective layer in the light-receiving member used for the electrophotographic photoreceptor and the like, and to achieve the above-mentioned object of the present invention. We have found that the structure of the BN thin film used as the protective layer is an important factor.

That is, in a boron nitride single crystal, two types of structures are known, a hexagonal system in which the coordination number of constituent elements is 3 and a cubic system in which the coordination number of constituent elements is 4.

The present inventors, when using a thin film composed of boron nitride as a surface protective layer of a light-receiving member used for an electrophotographic photoreceptor, continued to study how the structure of the boron nitride affects, It was found that boron nitride having any structure is not used as a surface protective layer, and boron nitride having a structure having a specific coordination number is suitable.

That is, a hexagonal crystal having a coordination number of 3 has the same structure as Braphyte, is very soft, and has a Mohs hardness of 2. Therefore, when it is used as a surface protective layer, corona discharge It has been found that it is vulnerable to the impact of active substances such as ions, ozone, and electrons generated by the above, and is deteriorated by various mechanical damages such as contact with a cleaning blade. Further, since the resistance value of the hexagonal crystal structure is relatively small, the light receiving member using this as a surface protective layer has a small charging ability, which causes deterioration of the quality of the formed image. Was also found.

On the other hand, those having a cubic structure in which the coordination number of the constituent elements is 4 have a large hardness, have sufficient resistance to corona discharge and mechanical shock, and further have resistance. Since the value is large, it has been found that when used as a material for forming the surface protective layer, a light receiving member having sufficient charging ability and capable of forming a good image can be obtained.

Therefore, from the viewpoint of strength alone, it is preferable that the surface protective layer is made of a non-single crystalline material containing boron nitride having a four-coordinate structure.

By the way, the image formation using the electrophotographic method 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 and formed on the paper largely depends on the quality of contact between the member used in each process and the surface of the light receiving member. For example, when considering a cleaning process using a blade, as one example, if the surface of the light receiving member is too hard, the blade will wear quickly and a cleaning failure is likely to occur. Further, the life of the blade is shortened, so that the maintenance cost of the copying machine is increased. On the other hand, if the surface of the light receiving member is too soft, the surface of the light receiving member is likely to be scraped by the blade, the image formed will have many image defects, and the life of the light receiving member will be shortened. The maintenance cost of the machine becomes high.

As described above, it is necessary to determine the surface hardness of the light receiving member in consideration of the balance with the hardness of various members that come into contact with each other in various processes, and the extremely hard four-coordinate structure boron nitride as described above is used. When it is used as a surface protective layer of a light receiving member, further improvement is required for each member in each process of image formation by electrophotography.

As a result of further research based on these findings, the present invention uses a thin film made of a non-single crystalline material containing only a tetracoordinated boron nitride as a lower surface protective layer and a 4-layered upper surface protective layer. When a thin film made of a non-single crystalline material containing a mixed structure of boron nitride and a tricoordinated structure of boron nitride mixedly is used, it is well balanced with various members used in each process. It has been found that an electrophotographic light-receiving member having a surface hardness and an excellent charging ability can be obtained.

Further, the present inventors have further studied the case of using a surface protective layer having a two-layer structure, and by incorporating a valence electron control agent into the surface protective layer, It has been found that a photoreceptor member is obtained which prevents charge accumulation after image exposure and has no image deletion or residual potential.

That is, when used as a light-receiving member for electrophotography, when charges are accumulated in the surface layer of the light-receiving member after image exposure, the accumulated charges move horizontally near the interface between the surface layer and the photoconductive layer to form It appears as an image flow in the image, but
In the light-receiving member of the present invention, by incorporating a valence electron control agent in the surface protective layer, the electric charge transferred into the surface protective layer after image exposure can be transferred to the free surface of the surface protective layer. Therefore, it is possible to prevent image deletion and residual potential generation.

The present invention has been completed based on these findings, and the essence of the invention is that a support and, on the support, a silicon atom as a host, and at least a hydrogen atom or a halogen atom. In a photoreceptive member comprising a photoconductive layer composed of an amorphous material containing one of them and a photoreceptive layer having at least a surface protective layer, the surface protective layer comprises only boron nitride having a four-coordinate structure. A lower surface layer composed of a non-single crystalline material containing 4
The upper surface layer is composed of a non-single crystalline material containing a mixture of boron nitride having a coordination structure and boron nitride having a tricoordination structure, and Si, S as a valence electron control agent.
The light-receiving member is characterized by containing n, Ge or Zn.

The light receiving member provided by the present invention is characterized by its surface protective layer, and not only the support,
Other constituent layers including the photoconductive layer can be arbitrarily selected according to the purpose of use. Therefore, a typical example of the layer structure of the light-receiving member of the present invention will be described below for electrophotography, but the light-receiving member of the present invention is not limited thereto.

FIGS. 1 (A) to 1 (I) are diagrams schematically showing typical examples of the layer structure of the light receiving member of the present invention used for electrophotography.

In the example shown in FIG. 1 (A), the photoconductive layer 102 is formed on the support 101.
And a surface protective layer 103 provided in this order, the surface protective layer 103 has a two-layer structure of a lower surface layer 103 and an upper surface layer 103, and the upper surface layer 103 has a free surface 107. There is.

In the example shown in FIG. 1 (B), a charge injection blocking layer 104, a photoconductive layer 102, and a surface protective layer 103 are provided in this order on a support 101.

In the example shown in FIG. 1 (C), a long-wavelength light absorption layer 105, a photoconductive layer 102, and a surface protective layer 103 are provided in this order on a support 101.

In the example shown in FIG. 1 (D), on the support 101, the adhesion layer 106,
The photoconductive layer 102 and the surface protective layer 103 are provided in this order.

The example shown in FIG. 1 (E) is the charge injection blocking layer 104, the adhesion layer 1
06, the photoconductive layer 102 and the surface protective layer 103 are provided in this order. The example shown in the first (F) is the long wavelength light absorption layer 10
5, the adhesion layer 106, the photoconductive layer 102, and the surface protective layer 103 are provided in this order.

In the example shown in FIG. 1 (G), a long-wavelength light absorption layer 105, a charge injection blocking layer 104, a photoconductive layer 102, and a surface protective layer 103 are provided in this order on a support 101. In the above, the order of the long wavelength light absorption layer 105 and the charge injection blocking layer 104 can be changed.

In the example shown in FIG. 1 (H), a long wavelength light absorption layer 105, a charge injection blocking layer 104, a photoconductive layer 102 and a surface protective layer 103 are provided in this order on a support 101. In the example shown in FIG. 1 (I), the charge injection blocking layer 104 and the photoconductive layer are provided on the support 101.
102, the intermediate layer 108, and the surface protective layer 103 are provided in this order.

The support 101 used in the light receiving member of the present invention may be either conductive or electrically insulating.
As the conductive support, for example, NiCr, stainless steel, A
Examples thereof include metals such as l, Cr, Mo, Au, Nb, Ta, V, Ti, Pt and Pb, and alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide, glass, ceramic, paper and the like. It is preferable that at least one surface of these electrically insulating supports is subjected to a conductive treatment, and a light receiving layer is provided on the surface side subjected to the conductive treatment.

For example, glass is NiCr, Al, Cr, M on the surface.
o, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, InO ₃ , ITO (In ₂ o
₃ + Sn) to provide conductivity, or synthetic resin film such as polyester film, NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, M
A thin film of a metal such as o, Ir, Nb, Ta, V, Tl, or Pt is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering or the like, or the surface is laminated with the above metal to conduct electricity to the surface. Imparts sex. The shape of the support may be a plate-shaped endless belt having a smooth surface or an uneven surface, a cylindrical shape, or the like, and the thickness thereof is appropriately determined so that a desired light-receiving member can be formed. When flexibility as a member is required, it can be made as thin as possible within a range in which the function as a support is sufficiently exhibited. However, in view of manufacturing the support, handling, mechanical strength, etc., it is usually 10 μm or more.

In the light receiving member of the present invention shown in FIG. 1 (B), the charge injection blocking layer 10 provided between the support 101 and the photoconductive layer 102.
Reference numeral 4 is a layer provided to prevent charges from being injected into the photoconductive layer 102 from the support side when it is subjected to a charging treatment with the photoconductive layer 102, and the charge injection blocking layer 104 is a -S
i (H, X) or polycrystalline silicon (hereinafter “poly-Si (H, X,
X) ”. ), Or so-called non-single-crystal silicon containing both (hereinafter referred to as “Non-Si (H, X)”) [Note that what is commonly referred to as microcrystalline silicon is a
-Classified as Si. ], An atom belonging to Group III of the periodic table (hereinafter simply referred to as "Group III atom") or an atom belonging to Group V of the periodic table (hereinafter simply referred to as "Group V atom"). It is made up of those containing.

The Group III atoms contained in the charge injection blocking layer 104 are specifically B (boron), Al (aluminum), Ga
(Gallium), In (indium), Tl (thallium) and the like can be used, but B and Ga are particularly preferable. Further, as the group V atom, specifically, P
(Phosphorus), As (arsenic), Sb (antimony), Bi (bismuth) and the like can be used, but P and As are particularly preferable. The amount of the group III atom or the group V atom 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 × 10 ^{2 to} 5
× 10 ³ atomic ppm is desirable.

The amount of halogen atoms or hydrogen atoms contained in the charge injection blocking layer 104 is set to 1 × 10 ^{3 to} 7 × 10 ⁵ atomic ppm, and particularly when it is composed of poly-Si (H, X). It is preferably 1 × 10 ^{3 to} 2 × 10 ⁵ atomic ppm, and a-Si (H, X)
When it is composed of, it is desirable to set 1 × 10 ^{4 to} 6 × 10 ⁵ atomic ppm. Further, the layer thickness of the charge injection blocking layer 104 of the light receiving member of the present invention is 0.03 to 15μ, preferably 0.04 to 10 μm.
μ, optimally 0.05 to 8 μ is desirable.

In the light receiving member of the present invention shown in FIG. 1 (C), a long wavelength light absorbing layer provided between the support 101 and the photoconductive layer 102.
105 is a layer composed of Non-Si (H, X) containing at least one of germanium atom (Ge) and tin atom (Sn), and uses long-wavelength light such as laser light as an exposure light source. In this case, the long-wavelength light absorption layer 105 efficiently absorbs the long-wavelength light that could not be absorbed in the photoconductive layer 102, and the interference phenomenon due to the reflection of the long-wavelength light on the surface of the support 101 appears. Has a function of remarkably preventing And the amount of Ge atoms or the amount of Sn atoms or the sum thereof contained in the long-wavelength light absorption layer 105 is 1 to 10 ⁶ a
tomic ppm, preferably 1 × 10 ^{2 to} 9 × 10 ⁵ atomic ppm,
More preferably, it is set to 5 × 10 ² to 8 × 10 ⁵ atomic ppm. The amount of hydrogen atoms or halogen atoms contained in the long wavelength light absorbing layer 105 is preferably 1 × 10 ³
~ 3 × 10 ⁵ atomic ppm is desirable, especially poly-
In the case of Si (Ge, Sn) (H, X), preferably 1 × 10 ³ to 2 × 10 ⁵
Atomic ppm is preferably set to 1 × 10 ^{4 to} 6 × 10 ⁵ atomic ppm in the case of a-Si (Ge, Sn) (H, X).

Further, the layer thickness of the long wavelength light absorption layer 105 in the light receiving member of the present invention is 0.05 to 25 μ, preferably 0.07 to 20 μ, and most preferably 0.1 to 15 μ.

In the light receiving member of the present invention shown in FIG. 1 (D), the adhesion layer 106 provided between the support 101 and the photoconductive layer 102 is
A layer having a function of improving the adhesion between the support 101 and the photoconductive layer 102, which contains at least one selected from oxygen atom, carbon atom or nitrogen atom.
(H, X) (hereinafter referred to as “Non-Si (O, C, N) (H, X)”). The amount of oxygen atoms, carbon atoms, and nitrogen atoms contained in the adhesion layer 106, or the sum of at least two of them is 100 to 9 × 10 ⁵ atomic p.
pm It is desirable to set it to 100 to 4 × 10 ⁵ atomic ppm. The amount of hydrogen atoms or halogen atoms contained in the adhesion layer 106 or the sum thereof is preferably 10
〜7 × 10 ⁵ atomic ppm, especially poly-Si (O, C, N) (H,
X) is 10 to 2 × 10 ⁵ atomic ppm, a-Si (O, C,
In the case of N) (H, X), it is desirable to set the concentration to 1 × 10 ^{3 to} 7 × 10 ⁷ atomic ppm.

By the way, the charge injection blocking layer in the light receiving member of the present invention
104, the long wavelength light absorption layer 105 and the adhesion layer 106 can be used in combination, and typical examples thereof are shown in FIGS. 1 (E) to (H).

Further, in the light receiving member of the present invention, the charge injection blocking layer
By containing at least one selected from oxygen atoms, carbon atoms and nitrogen atoms in 104 or long wavelength light absorption layer 105, it is also possible to have these layers also function as an adhesion layer, Also, long-wavelength light absorption layer
105 contains a Group III atom or a Group V atom, or
Alternatively, by incorporating germanium atoms or tin atoms in the charge injection blocking layer 104, it is possible to form a layer having the functions of both layers.

By the way, the charge injection blocking layer in the light receiving member of the present invention
104, the long wavelength light absorption layer 105 and the adhesion layer 106 are made of Non-Si (H,
X) is the base material, but poly-Si (H,
There are various methods for forming the layer composed of X), and for example, the following method can be mentioned.

One of the methods is to raise the substrate temperature to a high temperature, specifically 400 to 4
This is a method of setting a temperature of 50 ° C. and depositing a film on the substrate by a plasma CVD method.

Another method is to first form an amorphous film on the surface of the substrate, that is, plasma C on the substrate whose substrate temperature is about 250 ° C.
In this method, a film is formed by the VD method, and the amorphous film is annealed to form a poly. The annealing treatment is carried out 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 layer composed of a-Si (H, X) or a-Si (Ge, Sn) (H, X) and having photoconductivity. The layer may further contain at least one selected from Group III atoms or Group V atoms and / or oxygen atoms, carbon atoms and nitrogen atoms.

Specific examples of the halogen atom (X) contained in the photoconductive layer 102 include fluorine, chlorine, bromine and iodine, with fluorine and chlorine being particularly preferable. The amount of hydrogen atoms (H) or the amount of halogen atoms (X) or the sum of the amounts of hydrogen atoms and halogen atoms (H + X) contained in the photoconductive layer 102 is preferably 1 to 40 atomic%, more preferably 5 It is desirable to set it to ~ 30 atomic%. Further, the purpose of incorporating a group III atom atom or a group V atom into the photoconductive layer 102 is to control the conductivity of the photoconductive layer 102. As such a group III atom and a group V atom, the same ones as those contained in the above-mentioned charge injection blocking layer 104 can be used. An amount of the opposite polarity to that contained in the injection blocking layer 104 is contained, or an amount of the same polarity as that contained in the charge injection blocking layer 104 is much smaller than that contained in the layer 104. It can be included in the above.

The amount of the group III atom or the group V atom contained in the photoconductive layer 102 is preferably 1 × 10 ⁻³ to 1 × 10 ³ atomic ppm,
It is more preferably 5 × 10 ^{−2 to} 5 × 10 ² atomic ppm, and most preferably 1 × 10 ⁻¹ to 2 × 10 ² atomic ppm.

Further, in the photoconductive layer 102, the purpose of containing at least one selected from oxygen atom, carbon atom and nitrogen atom, while aiming at high dark resistance of the photoconductive layer 102, the film quality of the photoconductive layer 102. To improve. And
The amount of such atoms contained in the photoconductive layer 102 is preferably 1 × 10 ^{−3 to} 50 atomic%, more preferably 2 × 10 ^−3.
-40 atomic%, optimally 3 x ^{10-3 to} 30 atomic% is desirable.

Furthermore, in the photoconductive layer 102, at least one of germanium atom (Ge) and tin atom (Sn) can be contained. The purpose of containing such an atom is
The purpose is to improve sensitivity to long-wavelength light such as laser light, and in this case, the amount of these atoms to be contained in the photoconductive layer 102 is preferably 1 to 9.5 × 10 ⁵ atomic p.
pm is preferred.

Further, 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 the light receiving member is provided with desired characteristics. As described above, it is necessary to pay sufficient attention when designing the light receiving member, and usually 1 to 100 μm, but preferably 3 to 80 μm.
μ, optimally 5 to 50 μ.

The surface protective layer 103, which is characterized in the light receiving member of the present invention, is provided so as to be located on the photoconductive layer 102 described above.
It has a two-layer structure of a lower surface layer 103 in contact with the photosensitive layer 102 and an upper surface layer 103 provided on the lower surface layer,
The upper surface layer has a free surface 107. The surface protective layer 103 improves various characteristics required for the light receiving member, namely, moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability and the like, and It has a function of preventing charges from being injected into the photoconductive layer 102 from the free surface 107 side when subjected to a charging process.

The lower surface layer 103 ′ of the protective surface layer 103 of the light receiving member of the present invention which becomes harder is a non-single crystalline material containing boron nitride having a tetracoordinate structure [hereinafter referred to as “Non-BN”]. ], That is, an amorphous material [hereinafter referred to as “a-BN”]. ] Or a polycrystalline material [hereinafter referred to as "poly-BN". Or a mixture of both, the upper surface layer 103 ″ of the surface protective layer 103 is composed of Non-BN in which a four-coordinate structure and a three-coordinate structure are mixed, and the lower surface layer 103 ′ is And the upper surface layer 103 ″ contains a valence electron control agent. Further, the lower surface layer and the upper surface layer may contain at least one of a hydrogen atom and a halogen atom, if necessary. [Hereinafter, referred to as "Non-BN (H, X)" containing a hydrogen atom or a halogen atom. As the valence electron control agent contained in the surface protective layer 103 of the present invention, an n-type dopant capable of making the surface protective layer 103 n-type is used in the case of positive charging, and the surface protective layer 103 in the case of negative charging. Can be a p-type dopant. Specifically, silicon atoms (Si) or tin atoms (Sn) or mixtures thereof (Si) are used as n-type dopants.
+ Sn), and the p-type dopant includes germanium atom (Ge) or zinc atom (Zn) or a mixture thereof (Ge + Zn). And, the amount of the valence electron control agent contained in the surface protective layer is preferably 1000 atom.
ic ppm or less, more preferably 700 atomic ppm or less, and most preferably 500 atomic ppm.

Further, when the composition ratio of Non-BN (H, X) forming the surface protective layer 103 is represented by (B _x N _1-x ) _1-y · (H, X) _y , the following conditions are satisfied. Is desirable.

In the case of the lower surface layer made of non-BN having a four-coordinate structure, x: 0.25 ≦ x ≦ 0.75, preferably 0.3 ≦ x ≦ 0.7 optimally 0.4 ≦ x ≦ 0.6 y; 0.004 ≦ y ≦ 0.4 , Preferably 0.005 ≤ y ≤ 0.3 optimally 0.01 ≤ y ≤ 0.2 In the case of the upper surface layer made of Non-BN in which the four-coordinated structure and the three-coordinated structure are mixed, for x, 0.1 ≤ x ≤ 0.9, Preferably 0.2 ≤ x ≤ 0.8 Optimally for 0.3 ≤ x ≤ 0.7 y; 0.4 ≤ y ≤ 40, preferably 0.5 ≤ y ≤ 30 Optimally 1 ≤ y ≤ 20 Surface protection in the photoreceptor of the invention The layer thickness of the layer 103 is also one of the important factors for efficiently achieving the object of the present invention and is appropriately determined according to the desired purpose, but it is a constituent atom contained in the surface protective layer. It is necessary to make a mutual and organic correlation in accordance with the amount of the above, or the properties required for the surface protective layer. In addition, it is necessary to take into consideration the economical efficiency in consideration of productivity and mass productivity.

Therefore, the surface protective layer 10 of the light receiving member of the present invention is
The layer thickness of 3 is preferably 0.03 to 30μ, more preferably 0.0
04 to 20μ, optimally 0.005 to 10μ.

Further, in the light receiving member of the present invention, the above-mentioned surface protective layer
An intermediate layer 108 may be formed between 103 and the photoconductive layer 102. The intermediate layer 108 includes a-Si (H,
X) or poly-Si (H, X), and the intermediate layer 108
The amount of carbon atoms contained therein is preferably 20 to 90 at
omic%, more preferably 30-85 atomic%, optimally 40-
80 atomic% is desirable. 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 preferably 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 20 μm, optimally 0.005 to
10 μm is desirable.

Next, a method for forming the constituent layers of the light receiving member of the present invention will be described.

The non-single crystalline material that constitutes the light receiving member of the present invention is a glow discharge method (AC discharge CVD such as low frequency CVD, high frequency CVD or microwave CVD, or DC discharge CVD), sputtering method, vacuum deposition. It can be formed by various thin film deposition methods such as a method, an ion plating method, an optical CVD method, and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, a load level of capital investment, manufacturing scale, and characteristics desired for a light receiving member to be produced. The glow discharge method or the sputtering method is preferable because it is relatively easy to control the conditions for manufacturing the receiving member and the halogen atom and the hydrogen atom can be easily introduced together with the silicon atom. is there. Then, the glow discharge method and the sputtering method may be used together in the same apparatus system.

For example, by a glow discharge method, containing a valence electron control agent
To form a surface protective layer composed of Non-Si (H, X), basically, a source gas for supplying B, which can supply boron atoms (B), and a nitrogen atom (N) are supplied. To introduce the raw material gas for N supply and the silicon atom (Si) or / and tin atom (Sn) which is an n-type dopant or the germanium atom (Ge) or / and the zinc atom (Zn) which is a p-type dopant. Raw material gas and, if necessary, hydrogen atom (H)
A raw material gas for introducing and / or introducing a halogen atom (X) is introduced into a deposition chamber whose inside can be decompressed to cause glow discharge in the deposition chamber, and is composed of Non-BN (H, X). Form the layers.

As the raw material gas for supplying B, B ₂ H ₆ , B ₄ H ₁₀ B ₅ H ₉ , B ₅ H
Examples thereof include compounds in a gas state or gasifiable such as ₁₁ , B ₆ H ₁₂ , BF ₃ , and BCl ₃ .

Further, as the raw material gas for supplying N, N ₂ , NH ₃ , NF ₃ , N
Examples thereof include compounds in a gas state or gasifiable such as F ₂ Cl, NFCl ₂ , NCl ₃ , N ₂ F ₂ , N ₂ F ₄ , NH ₂ Cl, NHF ₂ and NH ₂ F.

As the raw material gas for introducing Si, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₆ , S
i ₄ H ₁₀ , SiF ₄ , SiCl _{4 and} other gas-state or gasifiable silicon compounds are mentioned, and the source gas for introducing Sn is
Examples thereof include tin compounds in a gas state or gasifiable such as SnH ₄ , SnF ₄ , and SnCl ₄ .

Further, as the raw material gas for introducing Ge, GeH ₄ , Ge ₂ H ₆ , G
Examples of the gas state or a gasifiable germanium compound such as eF ₄ , and the raw material gas for introducing Zn include Zn.
Examples thereof include (CH ₃ ) _{2 and} other gas-state or gasifiable zinc compounds.

Further, as a source gas for introducing a halogen atom, F ₂ , C
Halogen gas such as l ₂ , I ₂ , Br ₂ and FCl is used, and hydrogen gas and HF, HCl, HI, are used as raw material gases for introducing hydrogen atoms.
HBr, things like _{B 2 H 6, B 4 H} 10, NH 3, SiH 4, Si 2 H 6, SnH 4, GeH 4, Ge 2 which may or gasification of gaseous hydrogen compounds such as H ₆ .

Further, in order to form a lower surface layer consisting of a non-BN (H, X) layer having a four-coordinate structure containing a valence electron control agent by a sputtering method, a BN target is used as a target,
It is formed by introducing the B supply source gas together with an inert gas such as Ar into the deposition chamber to form a plasma atmosphere, and sputtering the BN target.

In addition, a non-BN (H, X) in which a 4-coordination structure containing a valence electron control agent and a 3-coordination structure are mixed by a sputtering method
As a target to form an upper surface layer consisting of
Using a BN target, the source gas for supplying N and the source gas capable of supplying the n-type dopant or the p-type dopant are Ar.
A raw material gas capable of supplying an n-type dopant or a p-type dopant by introducing into the deposition chamber together with an inert gas such as a plasma atmosphere to sputter the BN target or using a B target as a target, and the N It is formed by introducing a large amount of source gas for supply to form a plasma atmosphere and then sputtering the B target.

In order to form a layer composed of a-Si (H, X) by the glow discharge method, basically, silicon atoms (Si) are required.
Introducing a raw material gas for introducing hydrogen atoms (H) and / or introducing a halogen atom (X), together with a raw material gas for supplying Si, into a deposition chamber where the inside pressure can be reduced,
A glow discharge is generated in the deposition chamber to form a layer of a-Si (H, X) on the surface of a predetermined support placed in advance at a predetermined position. As the gas for supplying Si, SiH ₄ , Si
_{2 H 6, Si 3 H 8} , Si 4 silicon hydride that may or gasified gas state of H _10, etc. (silanes). In particular, the layer forming operation easiness, the and Si-feeding efficiency In this respect, SiH ₄ and Si ₂ H ₆ are preferable.

Further, as the source gas for introducing the halogen atom, many halogen compounds can be mentioned, for example, a halogen gas,
Gaseous or gasifiable halogen compounds such as halides, interhalogen compounds, silane derivatives substituted with halogen are preferred. Specifically, fluorine, chlorine, bromine,
Halogen gas of iodine, BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ , IF ₇ , I
Interhalogen compounds such as Cl and IBr, and SiF ₄ , Si ₂ F ₆ and SiC
Examples thereof include silicon halides such as l ₄ and SiBr ₄ . When a silicon halide in a gas state or gasifiable as described above is used, a layer composed of a-Si containing a halogen atom is formed without separately using a raw material gas for supplying Si. It is particularly effective because it can.

Further, as the raw material gas for supplying the hydrogen atoms, hydrogen gas, halides such as HF, HCl, HBr, HI, SiH ₄ , Si ₂ H ₆ , S
i ₃ H ₈ , Si ₄ H _10, etc., silicon hydride, or SiH ₂ F ₂ , SiH ₂ I ₂ , S
_{iH 2 Cl 2, SiHCl 3,} SiH 2 Br 2, SiHBr 3, shall be able to use that can or gasification of gaseous, such as a halogen-substituted silicon hydride etc., in the case of using these raw material gases, This is effective because it is possible to easily control the content of hydrogen atoms (H), which is extremely effective in controlling electrical or photoelectric characteristics. When the hydrogen halide or the halogen-substituted silicon hydride is used, a hydrogen atom (H) is introduced at the same time as the introduction of the halogen atom, which is particularly effective.

To form a layer of a-Si (H, X) by the reactive sputtering method or the ion plating method, for example, in the case of the sputtering method, for introducing a halogen atom, the above-mentioned halogen compound or the above is used. The silicon compound gas containing the halogen atom 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, for example, a gas such as H ₂ or the above-mentioned silanes is introduced into the deposition chamber for sputtering to form a plasma atmosphere of the gas. Good.

For example, in the case of the reactive sputtering method, a Si target is used, and a gas for introducing a halogen atom and an H ₂ gas are introduced into the deposition chamber, including an inert gas such as He and Ar as necessary, and a plasma atmosphere is obtained. And sputtering the Si target to form a-Si (H,
X) is formed.

In order to form a layer composed of a-SiGe (H, X) by the glow discharge method, a source gas for supplying Si, which can supply silicon atoms (Si), and a Ge, which can supply germanium atoms (Ge). A deposition chamber capable of reducing the pressure of the source gas for supply and the source gas for supplying hydrogen atom (H) and / or halogen atom (X) capable of supplying hydrogen atom (H) and / or halogen atom (X) Is introduced into the deposition chamber at a desired gas pressure, a glow discharge is caused to occur in the deposition chamber, and a layer composed of a-SiGe (H, X) is formed on the surface of a predetermined support previously installed at a predetermined position. To form.

Source gas for supplying Si, source gas for supplying halogen atoms,
As the substance that can be used as the raw material gas for supplying hydrogen atoms, those used when forming the layer composed of a-Si (H, X) described above are used as they are.

Further, as the substance that can be the raw material gas for supplying Ge, GeH ₄ , Ge ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , G
It is possible to use germanium hydride in the gas state or gasifiable such as e ₈ H ₁₈ , Ge ₉ H _{20 and the} like. In particular, from the viewpoints of ease of handling during layer formation work and good Ge supply efficiency, GeH ₄ , Ge
₂ H ₆ and Ge ₃ H ₈ are preferred.

To form a layer composed of a-SiGe (H, X) by the sputtering method, a target made of silicon and
The sputtering is performed by using two targets of germanium or by using a target of silicon and germanium in the desired gas atmosphere.

When the layer composed of a-SiGe (H, X) is formed by using the ion plating method, for example, polycrystalline silicon or single crystal silicon and polycrystalline germanium or also single crystal germanium are used as evaporation sources, respectively. It can be carried out by accommodating it in a vapor deposition boat, heating the evaporation source by a resistance heating method, an electron beam method (EB method), or the like, and allowing a flying evaporated material to pass through a desired gas plasma atmosphere.

In either case of the sputtering method and the ion plating method, in order to make the layer to contain a halogen atom, a gas of the above-mentioned halide or a silicon compound containing a halogen atom is introduced into the deposition chamber, and the gas is introduced. The plasma atmosphere may be formed. Further, when hydrogen atoms are introduced, a raw material gas for supplying hydrogen atoms, for example, H ₂ or the above-mentioned hydrogenated silanes and / or gases such as germanium hydride are introduced into the deposition chamber for sputtering. It suffices to form a plasma atmosphere of gases such as. Further, as the source gas for supplying halogen atoms, the above-mentioned halides or silicon compounds containing halogen can be mentioned as effective ones, but in addition, hydrogen halides such as HF, HCl, HBr and HI, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ B
halogen-substituted silicon hydrides such as r ₂ , SiHBr ₃ , etc., and GeH
_{F 3, GeH 2 F 2,} GeH 3 F, GeHCl 3, GeH 2 Cl 2, GeH 3 Cl, GeHBr 3, GeH 2 B
r ₂ , GeH ₃ Br, GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I, etc.Hydrogenated halogenated germanium, etc., GeF ₄ , GeCl ₃ , GeBr ₄ , GeI ₄ , GeF ₂ , GeCl ₂ , GeB
Gaseous or gasifiable substances such as r ₂ , germanium halides such as GeI _2, etc. can also be used as effective starting materials.

Amorphous silicon containing tin atoms (hereinafter, referred to as "a-SiSn (H, X)") using a glow discharge method, a sputtering method, or an ion plating method.
In order to form a light receiving layer composed of
When forming a layer composed of (H, X), the starting material for supplying germanium atoms is used in place of the starting material for supplying tin atoms (Sn), and the amount thereof in the layer to be formed is changed. This is done by controlling the content.

Examples of the tin atoms (Sn) can be a raw material gas for the feed material, tin hydride (SnH ₄₎ or _{SnF 2, SnF 4, SnCl 2} , SnCl 4, Sn
Br ₂ , SnBr ₄ , SnI ₂ , SnI ₄ or the like can be used in a gas state or gasifiable such as tin halide, and when tin halide is used, a halogen atom is provided on a predetermined support. This is particularly effective because a layer composed of s-Si contained can be formed. Among them, SnCl ₄ is preferable from the viewpoints of ease of handling during layer formation work and good Sn supply efficiency.

When SnCl ₄ is used as a starting material for supplying tin atoms (Sn), solid SnCl ₄ can be used for gasification.
It is desirable to boil an inert gas such as Ar and He while heating and bubbling using the inert gas.The gas thus generated is introduced into the deposition chamber whose inside pressure is reduced in a desired gas pressure state. To do.

Amorphous material in which a-Si (H, X) contains a Group III atom or a Group V atom, a nitrogen atom, an oxygen atom or a carbon atom by using a glow discharge method, a sputtering method, or an ion plating method. To form a layer composed of a material, a starting material for introducing a group III atom or a group V atom and a starting material for introducing an oxygen atom at the time of forming a layer of a-Si (H, X) , A starting material for introducing a nitrogen atom, or a starting material for introducing a carbon atom together with the above-mentioned starting material for forming a-Si (H, X), and controlling their amounts in the layer to be formed. However, it is done by including it.

For example, in order to form a layer composed of a-Si (H, X) containing atoms (O, C, N) using the glow discharge method, the above-mentioned a-Si (H, X) is used. Amounts of the starting materials for introducing atoms (O, C, N) together with the starting materials for forming a-Si (H, X) in forming the layers to be formed Is carried out by controlling the content.

As a starting material for introducing such an atom (O, C, N),
Most substances can be used as long as they are gaseous substances or substances that can be gasified and have at least atoms (O, C, N) as constituent atoms.

Specifically, as a starting material for introducing an oxygen atom (O), for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO),
Nitrogen monoxide (N ₂ O), Trinitrogen dioxide (N ₂ O ₃ ), Nitrogen dioxide (N ₂ O ₄ ), Nitrogen pentaoxide (N ₂ O ₅ ), Nitric oxide (NO ₃ ), Silicon atom ( Si), oxygen atom (O), and hydrogen atom (H) as constituent atoms, such as disiloxane (H ₃
Examples thereof include lower siloxanes such as SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). Examples of the starting material for introducing a carbon atom (C) include methane (CH ₄ ) and ethane (C ₂ H
_6), propane (C ₃ H _8), n- butane _{(n-C 4 H 10)} , pentane (C ₅ H ₁₂₎ saturated hydrocarbons having 1 to 5 carbon atoms such as 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., an ethylene hydrocarbon having 2 to 5 carbon atoms, acetylene (C ₂ H ₂ ), Methylacetylene (C ₃ H ₄ ),
Examples include acetylene hydrocarbons having 2 to 4 carbon atoms such as butyne (C ₄ H ₆ ), and the starting materials for introducing the nitrogen atom (N) include, for example, nitrogen (N ₂ ) and ammonia (NH ₃ ). , Hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen trifluoride (F ₃ ), nitrogen tetratrifluoride (F
₄ N).

For example, when the glow discharge method is used to form a layer or a layer region containing an oxygen atom, one selected from the above-mentioned starting materials for forming the light receiving member layer as desired for introducing an oxygen atom is used. Starting material is added. As such a starting material for introducing an oxygen atom, almost any material can be used as long as it is a gaseous substance containing at least an oxygen atom as a constituent atom or a gasifiable substance.

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing oxygen atoms (O) as constituent atoms, and, if necessary, hydrogen atoms (H) and / or halogen atoms (X).
Or a raw material gas having a constituent atom is used at a desired mixing ratio, or a raw material gas having a silicon atom (Si) as a constituent atom and an oxygen atom (O) and a hydrogen atom (H) are constituted. A raw material gas containing atoms is also mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) as constituent atoms, and silicon atoms (Si), oxygen atoms (O) and hydrogen atoms. It is possible to mix and use a raw material gas containing three of (H) as constituent atoms.

Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) 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 monoxide (N ₂ ).
₂ O), nitrogen trioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ) nitrogen dioxide (N ₂ O ₅ ), nitric oxide (NO ₃ ), silicon atom (Si) and oxygen atom ( Examples thereof include lower siloxanes having O) and a hydrogen atom (H) as constituent atoms such as disiloxane (H ₃ SiOSiH ₃ ), trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ), and the like.

To form a layer or layer region containing oxygen atoms by a sputtering method, a single crystal or Si wafer or Si is used.
This may be carried out by using an O ₂ wafer or a wafer containing Si and SiO ₂ as a mixture as a target and sputtering these in various gas atmospheres.

For example, if a Si wafer is used as a target, a raw material gas for introducing oxygen atoms and, if necessary, hydrogen atoms and / or halogen atoms is diluted with a diluent gas as needed, and then is placed in a deposition chamber for sputtering. The Si wafer may be sputtered by introducing it, forming gas plasma of these gases.

Also, as a separate target for Si and SiO ₂ , or
By using a single target in which Si and SiO ₂ are mixed, it contains at least a hydrogen atom (H) or / and a halogen atom (X) as a constituent atom in an atmosphere of a diluent gas for sputtering. It can be formed by sputtering in a gas atmosphere. As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the example of glow discharge described above can be used as an effective gas in the case of sputtering.

Further, for example, in order to form a layer composed of amorphous silicon containing carbon atoms by a glow discharge method, a raw material gas containing silicon atoms (Si) as a constituent atom and a raw material containing carbon atoms (C) as a constituent atom. A gas and a raw material gas containing hydrogen atoms (H) and / or halogen atoms (X) as constituent atoms are mixed at a desired mixing ratio and used, or silicon atoms (Si) are constituent atoms. And a raw material gas containing carbon atoms (C) and hydrogen atoms (H) as constituent atoms, which are also mixed at a desired mixing ratio, or silicon atoms (Si) are formed. A raw material gas having atoms and a raw material gas having silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H) as constituent atoms are mixed or
Furthermore, raw material gases containing silicon atoms and hydrogen atoms as constituent atoms are mixed and used.

Effectively used as such a raw material gas is hydrogenation of silanes such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ Si ₄ H ₁₀ having Si and H as constituent atoms. Examples thereof include silicon gas, C and H as constituent atoms, for example, saturated hydrocarbons having 1 to 4 carbon atoms, ethylene hydrocarbons having 2 to 4 carbon atoms, and acetylene hydrocarbons having 2 to 3 carbon atoms.

Specifically, as the saturated hydrocarbon, for example, 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 ), ethylene-based hydrocarbons such as 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 ) acetylene-based hydrocarbons include acetylene (C ₂ H ₂ ), Methyl acetylene (C ₃
H ₄ ), butyne (C ₄ H ₆ ) and the like.

As a source gas containing Si, C and H as constituent atoms, Si (C
Mention may be made of alkyl silicides such as H ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ . In addition to these raw material gases, H ₂ can of course be used as the raw material gas for introducing H.

In order to form a layer composed of a-SiC (H, X) by the sputtering method, a single crystal or polycrystal Si wafer or C (graphite) wafer or a wafer in which Si and C are mixed is used as a target. , And these are sputtered in a desired gas atmosphere.

For example, in the case of using a Si wafer as a target, a raw material gas for introducing carbon atoms, and / or 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 the gas plasma of these gases into the deposition chamber.

Separately, when Si and C are used as separate targets, or when used as a single target in which Si and C are mixed, a raw material for introducing hydrogen atoms and / or halogen atoms as a gas for sputtering is used. The gas may be diluted with a diluent gas, if necessary, and introduced into a deposition chamber for sputtering to form a gas plasma for 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 can be used as it is.

For example, when the glow discharge method is used to form a layer or a layer region containing a nitrogen atom, a starting material for introducing a nitrogen atom is selected from the above-mentioned starting materials for forming the light-receiving layer as desired. Add substance. As such a starting material for introducing a nitrogen atom, almost any material can be used as long as it is a gaseous substance containing at least a nitrogen atom as a constituent atom or a substance that can be gasified.

For example, a raw material gas containing silicon atoms (Si) as constituent atoms, a raw material gas containing nitrogen atoms (N) as constituent atoms, and, if necessary, hydrogen atoms (H) and / or halogen atoms (X).
Or a raw material gas containing Si as a constituent atom is mixed at a desired mixing ratio, or a raw material gas containing a silicon atom (Si) as a constituent atom and a nitrogen atom (N) and a hydrogen atom (H) are composed. Atomic source gas may also be mixed or used in a desired mixing ratio.

Alternatively, a raw material gas containing silicon atoms (Si) and hydrogen atoms (H) as constituent atoms may be mixed with a raw material gas containing nitrogen atoms (N) as constituent atoms.

A starting material effectively used as a raw material gas for introducing a nitrogen element (N) used when forming a layer or a layer region containing a nitrogen atom is N as a constituent atom or N and H.
With and as constituent atoms, such as nitrogen (N ₂ ), ammonia (NH
₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ) and other gaseous or gasifiable nitrogen compounds, nitrogen compounds such as boron nitrides and azides. Can be mentioned. In addition to these, halogenated nitrogen compounds such as nitrogen trifluoride (F ₃ N) and tetratetrafluoride (F ₄ N) can be introduced in addition to the introduction of nitrogen atoms. Can be mentioned.

By a sputtering method, to form a layer or layer region containing a nitrogen atom, a single crystal or Si wafer or a polycrystalline Si wafer, or Si ₃ N ₄ wafer, or Si and Si ₃
A wafer containing H ₄ mixed therein may be used as a target to perform sputtering in various gas atmospheres.

For example, when a Si wafer is used as a target, a raw material gas for introducing nitrogen atoms and, if necessary, hydrogen atoms and / or halogen atoms is diluted with a diluting gas, if necessary, and then deposited in a deposition chamber for sputtering. The Si wafer may be sputtered by introducing gas into them and forming gas plasma of these gases.

Alternatively, Si and Si ₃ N ₄ are used as separate targets, or by using a single target in which Si and Si ₃ N ₄ are mixed, in a diluting gas atmosphere as a gas for sputtering or It can be formed 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 in the raw material gas showing the example of glow discharge described above,
It can also be used as an effective gas in the case of sputtering.

Further, when a layer composed of a-Si (H, X) containing a group III atom or a group V atom is formed by glow discharge method, sputtering method or ion plating method, Using a starting material for introducing a Group III atom or a Group V atom together with a starting material for forming a-Si (H, X),
It is carried out by controlling the amount of them to be contained in the layer to be formed.

Specifically as a starting material for introducing a Group III atom, for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H
Examples thereof include boron hydride such as ₁₂ and B ₆ H ₁₄ , and boron halide such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga (C
_{H 3) 2, InCl 3,} TlCl 3 , etc. can also be mentioned.

As a starting material for introducing a group V atom, specifically, for introducing a phosphorus atom, a hydrogenated phosphorus such as PH ₃ , P ₂ H ₆ or the like PH ₄ I, PF ₃ , PF ₅ , PCl ₃ ,
Phosphorus halides such as PCl ₅ , PBr ₃ , PBr ₅ and PI ₃ can be mentioned. In addition, AsH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ , Sb
Cl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr _{5 and the} like can also be mentioned as effective starting materials for introducing a Group V atom.

As described above, the light-receiving layer of the light-receiving member of the present invention is formed by using the glow discharge method, the sputtering method, or the like.
And a tin atom, a group III atom or a group V atom, an oxygen atom, a carbon atom or a nitrogen atom, or a hydrogen atom or /
The content of each of the halogen atoms and the halogen atoms is controlled by controlling the gas flow rate of each atom supplying starting material or the gas flow rate ratio between each atom supplying starting material flowing into the deposition chamber.

The conditions such as the temperature of the support, the gas in the deposition chamber, and the discharge power at the time of forming each constituent layer such as the photoconductive layer and the surface protective layer are
This is an important factor for obtaining a light receiving member having desired characteristics, and is appropriately selected in consideration of the function of the layer to be formed. Further, these layer forming conditions may differ depending on the type and amount of each of the above-mentioned atoms contained in each constituent layer such as the photoconductive layer and the surface protective layer. It is also necessary to make a decision with due consideration.

Specifically, a non-coordinated four-coordinate structure containing a valence electron control agent
When the lower surface layer made of BN (N, X) is formed by the high frequency (13.56MHz) plasma CVD method, the gas pressure in the deposition chamber is usually 10 ^{-2 to} 10 Torr, more preferably 5 x 10
^{2 to 2} Torr, optimally 0.1 to 1 Torr. The temperature of the support is usually 50 to 700 ° C., but especially 50 to 400 ° C. in the case of the Non-BN (N, X) layer, and the poly-BN (H, X) layer. 200-700 ℃ Furthermore, the discharge power is usually 0.01 ~
5W / cm ^2, more preferably from 0.02~2W / cm ^2. Furthermore, the gas flow rate ratio of the B supply source gas, the N supply source gas and the Ar gas is such that B / N is 1/5 to 100/1, more preferably 1/4 to
It is 80/1, and Ar / B + N is 1/10 to 100/1, and more preferably 1/7 to 80/1.

In addition, the non-BN (H,
When the lower surface layer consisting of X) is formed by the microwave (2.45 GHz) plasma CVD method, the gas pressure in the deposition chamber is usually 1
0 ^-4 ~2Torr, and more preferably 5 × 10 ^-4 ~1.0Torr, and optimally with 5 × 10 ^-4 ~0.7Torr, discharge power is usually from 0.1 to 50
W / cm ^2, more preferably from 0.2~30W / cm ^2. The support temperature and the gas flow rate ratio of each raw material gas are the same as in the case of the above-described high frequency plasma CVD method.

Furthermore, a non-BN (H,
When the lower surface layer composed of X) is formed by the sputtering method, the gas pressure in the deposition chamber is usually 10 ^{−4 to 1} Torr, more preferably 5 × 10 ^{−4 to} 0.7 Torr, and the discharge power is 0.0.
It is 1 to 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 above-mentioned high frequency plasma CVD method.

In addition, when the upper surface layer made of Non-BN (H, X) in which a 4-coordination structure containing a valence electron control agent and a 3-coordination structure are mixed is formed by a high frequency (13.56 MHz) plasma CVD method,
The gas pressure in the deposition chamber is usually 10 ^{−2 to} 10 Torr, more preferably 5 × 10 ^{2 to 2} Torr, most preferably 0.1 to 1 Torr. In addition, the support temperature is usually 50 to 700 ° C, but especially in the case of a Non-BN (H, X) layer, 50 to 400 ° C, poly-B
When the N (H, X) layer is used, 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 rate ratio of the B supply source gas, the N supply source gas, and the Ar gas is such that B / N is 1 to 100 to 5/1,
More preferably, it is 1/80 to 4/1 and Ar / B + N is 1
It should be / 1 to 0.

Further, when the upper surface layer made of Non-BN (H, X) in which a 4-coordination structure containing a valence electron control agent and a 3-coordination structure are mixed is formed by a high frequency (2.45 GHz) plasma CVD method, The gas pressure in the room is usually 10 ^{-4 to 2} Torr, more preferably 5 x 1
0 ^{-4 to} 1.0 Torr, optimally 5 x 10 ^{-4 to} 0.7 Torr, discharge power is usually 0.1 to 50 W / cm ² , more preferably 0.2 to 30 W / c
m ² The support temperature and the gas flow rate ratio of each source gas are
Both are the same as in the case of the above-mentioned high-frequency plasma CVD method.

Furthermore, when the upper surface layer made of Non-BN (H, X) in which a 4-coordination structure containing a valence electron control agent and a 3-coordination structure are mixed is formed by the sputtering method, the gas pressure in the deposition chamber is usually 10 ^{−4 to 1} Torr, more preferably 5 × 10 ^{−4 to} 0.7 Torr,
And the discharge power is 0.01 to 10 W / cm ² , more preferably 0.0.
5 to 8 W / cm ² . The support temperature is the above-mentioned high-frequency plasma C
This is the same as in the VD method.

When a layer made of a-Si (H, X) containing a nitrogen atom, an oxygen atom, a carbon atom, etc. is formed by the glow discharge method, the support temperature is usually 50 to 350 ° C. The temperature is preferably 50 to 250 ° C. Gas pressure in the deposition chamber is usually
The pressure is 0.01 to 1 Torr, and particularly preferably 0.1 to 0.5 Torr. The discharge power is usually 0.005 to 50 W / cm ² , but more preferably 0.01 to 30 W / cm ² . It is particularly preferably 0.01 to 20 W / cm ² .

When the a-SiGe (H, X) layer is formed by the glow discharge method, or when the layer formed of a-SiGe (H, X) containing a group III atom or a group V atom is formed, The temperature of the support is usually 50 to 350 ° C, more preferably 50 to 300 ° C, and particularly preferably 100 to 300 ° C. And the gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.001 to 3 Torr, particularly preferably 0.
01 to 1 Torr. Also, the discharge power is 0.005 to 50 W / cm ²
It is usually set to 0.01 to 30 W / cm ² . It is particularly preferably 0.01 to 20 W / cm ² .

However, the specific conditions of the temperature of the support, the discharge power, and the gas pressure in the deposition chamber for forming layers are usually difficult to determine individually.
Therefore, in order to form an amorphous material layer having desired characteristics,
It is desirable to determine the optimum conditions for layer formation based on mutual and organic relationships.

Next, a method for manufacturing a photoconductive member formed by the glow discharge decomposition method will be described.

FIG. 2 shows an apparatus for producing a light receiving member for electrophotography by the glow discharge decomposition method.

The gas cylinders 202, 203, 204, 205, 206, 241, and 247 in the figure are sealed with the raw material gas for forming the respective layers of the present invention. As an example, 202 is SiH.
₄ gas (99.999% purity) cylinder, 203 B ₂ was diluted with H ₂
H ₆ gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ / H ₂ ) cylinder, 2
04 is NO gas (purity 99.5%) cylinder, 205 is B ₂ H ₆ gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ / Ar) cylinder diluted with Ar, 206 is B ₂ H diluted with He ₆ gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ / He) cylinder, 241 is SiH ₄ gas (purity 99.999%, hereinafter abbreviated as SiH ₄ / He) cylinder, 247 is
NH ₃ gas (purity 99.999%) cylinder.

A gas cylinder 2 is used to allow these gases to flow into the reaction chamber 201.
Check that the valves 02-206, 241, 247 and the leak valve 235 are closed, and check the inflow valves 212-216, 24.
3, 249, outflow valves 217 to 221, 244, 250, auxiliary valve 23
Make sure that 2,233 is open, then first open the main valve.
234 is opened and the reaction chamber 201 and the gas pipe are exhausted. Next, when the reading of the vacuum gauge 236 reaches about 5 × 10 ⁻⁶ Torr, the auxiliary valves 232 and 233 and the outflow valves 217 to 221, 244 and 250 are closed.

As an example of forming the first layer on the base cylinder 237, SiH ₄ gas from gas cylinder 202, gas cylinder, B ₂ H ₆ / H ₂ gas from 203, gas cylinder, NO gas from 204, valve 222, 223, 224 open and outlet pressure gate 227, 22
Adjust the pressure of 8 and 229 to 1 kg / cm ^2, and adjust the inflow valves 212, 213 and 2
Gradually open 14 to open the mass flow controllers 207, 208, 20
Inflow into 9 Then the outflow valves 217, 218, 219,
The auxiliary valve 232 is gradually opened to allow each gas to flow into the reaction chamber. At this time, the outflow valve is adjusted so that the ratio of SiH ₄ gas flow rate, B ₂ H ₆ / H ₂ gas flow rate, NO gas flow rate becomes a desired value.
217, 218, 219 are adjusted, and the opening of the main valve 234 is adjusted while observing the reading of the vacuum gauge 236 so that the pressure in the reaction chamber becomes a desired value. Then, after it is confirmed that the temperature of the base cylinder 237 is set to a temperature of 50 to 350 ° C. by the heater 238, the power supply 240 is set to a desired power to cause glow discharge in the reaction chamber 201. A first layer is formed on the substrate cylinder.

When the first layer contains halogen atoms, SiF ₄ gas, for example, is further added to the above-mentioned gas and fed into the reaction chamber 201.

When forming each layer, the layer formation rate can be further increased depending on the selection of gas species. For example, instead of SiH ₄ gas, Si
_If a layer is formed using ₂ H ₆ gas, it can be increased several times, and productivity is improved.

To form the second layer on the first layer prepared as described above, the outflow valves 217-221, 244, 247 are closed, the auxiliary valves 232-233 are opened, and the main valve 234 is fully opened. After evacuating the inside of the system to a high vacuum, B ₂ H ₆ / Ar gas, B ₂ H ₆ / He gas, and B ₂ H ₆ / He gas by the same valve operation as when forming the first layer,
A gas containing an NH ₃ gas and a valence electron control agent, SiH ₄ / He gas of 241 in the example of FIG. 2, is flowed into the reaction chamber 101 at a desired flow rate ratio to cause glow discharge according to desired conditions. Made by

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 can be arbitrarily set as desired. Can be controlled as desired by changing to.

When the second layer contains halogen atoms, NF ₃ gas, for example, is further added to the above gas and fed into the reaction chamber 101.

It goes without saying that all the outflow valves other than the gas required for forming each layer are closed, and when forming each layer, the gas used for forming the previous layer is the outflow valve 217 in the reaction chamber 101. ~ 221 to avoid remaining in the pipe from the inside of the reaction chamber 101, the outflow valves 217 to 221 are closed, the auxiliary valves 232 and 233 are opened, the main valve 234 is fully opened, and the system is once evacuated to a high vacuum. Perform the operation as required.

Further, during the layer formation, in order to make the layer formation uniform, the substrate cylinder 237 is constantly rotated by the motor 239 at a desired speed.

〔Example〕

Hereinafter, the present invention will be described 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 an aluminum cylinder that was mirror-finished in accordance with the preparation conditions shown in Tables 1 (a) and 1 (b).

Separately, using a device of the same type as shown in FIG. 2, an aluminum substrate and a single crystal Si wafer are placed on a sample holder on a cylinder, and only an upper surface layer and a lower surface layer having the same specifications are respectively formed separately. I prepared it.

For the light receiving member (hereinafter referred to as a drum), set the electrophotographic device and check the electrophotographic characteristics such as initial charging ability, residual potential and ghost under various conditions.
We investigated the decrease in charging ability, surface scraping, and increase in image defects after the endurance of 1.5 million sheets. Further, the cleaner blade was intentionally replaced with one whose edge portion was rubbed, and the cleaning performance was compared depending on the degree of background fog on the solid white image. Furthermore, the image deletion of the drum in a high temperature and high humidity atmosphere of 35 ° C and 85% was also evaluated.

Further, the dielectric strength voltage was examined by applying a high DC voltage to the drum. Further, the scratch resistance was examined by applying a constant load to a needle having a spherical tip and scratching the drum surface. Table 2 shows the evaluation results.

As shown in Table 2, good results were obtained for all items. In particular, remarkable advantages were recognized in image defects, image deletion, withstand voltage, scratch resistance, and cleaning property (degree of background fog).

One with only upper and lower surface layers formed on aluminum substrate and single crystal Si wafer (hereinafter referred to as sample)
When the coordination number was investigated by EXAFS and IR respectively,
It was found that the lower surface layer was tetracoordinated and the upper surface layer was a mixture of tetracoordinated and tricoordinated.

Example 2 H ₂ gas was added to the raw material gas of the surface layer, and
Under the preparation conditions shown in (b), a drum and a sample were prepared and evaluated in the same manner as in Example 1.

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 the lower surface layer was tetracoordinated and the upper surface layer was a mixture of tricoordinated and tetracoordinated.

<Example 3> When the surface layer was formed, the cylinder bias voltage was set to -150V for the lower surface layer and + 100V for the upper surface layer in Tables 1 (a) and (b). Drums and samples were prepared under the preparation conditions shown in the same manner as in Example 1 and evaluated in the same manner.

The results are shown in Table 5.

As shown in Table 5, the same characteristics as in Example 1 were obtained.

Further, as a result of measuring the sample, it was found that the lower surface layer was tetracoordinated and the upper surface layer was a mixture of tricoordinated and tetracoordinated.

<Example 4> A drum was prepared in the same manner as in Example 1 except that the charge injection blocking layer, the photoconductive layer and the surface layer were prepared under the conditions shown in Tables 6 (a) and 6 (b), respectively, 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.

Performing anodic oxidation treatment <Example 5> aluminum cylinder, to create an aluminum oxide layer on the cylinder surface (Al ₂ O _3), which, as a charge injection blocking layer, a photoconductive layer on this layer Drums were prepared in the same manner as in Example 1 for the surface layer under the preparation conditions shown in Tables 8 (a) and 8 (b), and the same evaluation was performed.

The results are shown in Table 9.

As shown in Table 9, the same characteristics as in Example 1 were obtained.

<Example 6> The long wavelength light absorption layer (hereinafter referred to as "IR absorption layer"), the photoconductive layer, and the surface layer were formed under the conditions shown in Tables 10 (a) and 10 (b), respectively. A drum was prepared in the same manner as in No. 1, and the same evaluation was performed.

Further, 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 shown in Table 11, the same characteristics as in Example 1 were obtained and no interference fringes appeared.

<Example 7> The adhesion layer, the photoconductive layer, and the surface layer are respectively shown in Table 12 (a),
Under the production conditions shown in (b), a drum was produced in the same manner as in Example 1, and the same evaluation was performed.

The results are shown in Table 13.

As shown in Table 13, the same characteristics as in Example 1 were obtained.

<Example 8> The IR absorption layer, the charge injection blocking layer, the photoconductive layer, and the surface layer were formed under the conditions shown in Tables 14 (a) and 14 (b), respectively.
A drum was prepared in the same manner as in, and the same evaluation as in Example 6 was performed.

The results are shown in Table 15.

As shown 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 except that the adhesion layer, the charge injection blocking layer, the photoconductive layer, and the surface layer were prepared under the conditions shown in Tables 16 (a) and 16 (b). An evaluation was made.

The results are shown in Table 17.

As shown in Table 17, the same characteristics as in Example 1 were obtained.

<Example 10> The adhesion layer, the IR absorption layer, the charge injection blocking layer, the photoconductive layer and the surface layer were formed in the same manner as in Example 1 under the conditions shown in Tables 18 (a) and 18 (b), respectively. Was prepared and evaluated in the same manner as in Example 6.

The results are shown in Table 19.

As shown 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,
A plurality of drums were prepared under the same conditions as in Example 1 except for the above.

As a result of subjecting these drums to the same evaluation as in Example 1,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 1.

<Example 12> The conditions for forming the photoconductive layer were changed to several conditions shown in Table 21,
A plurality of drums were prepared under the same conditions as in Example 2 except for the above.

As a result of subjecting these drums to the same evaluation as in Example 2,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained in the same manner as in Example 2.

<Example 13> The conditions for forming the photoconductive layer were changed to several conditions shown in Table 22,
A plurality of drums were prepared under the same conditions as in Example 3 except for the above.

As a result of subjecting these drums to the same evaluation as in Example 3,
In each case, similarly to Example 3, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

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,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 4.

<Example 15> 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 25, and otherwise, Example 4 was used. A plurality of drums shown in Table 26 were prepared under the same conditions as in.

As a result of subjecting these drums to the same evaluation as in Example 4,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 4.

<Example 16> 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. Under the conditions shown in Table 28,
A plurality of drums shown in the table were prepared.

As a result of subjecting these drums to the same evaluation as in Example 4,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained 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. Under the conditions shown in Table 30, 31st
A plurality of drums shown in the table were prepared.

As a result of subjecting these drums to the same evaluation as in Example 4,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 4.

<Example 18> The conditions for forming the photoconductive layer were changed to several conditions shown in Table 25,
A plurality of drums shown in Table 32 were prepared under the same conditions as in Example 5 except for the above.

As a result of subjecting these drums to the same evaluation as in Example 5,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained in the same manner as in Example 5.

<Example 19> The conditions for forming 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 other conditions were the same as those in Example 5 A plurality of drums shown in Table 33 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 5,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained in the same manner as in Example 5.

<Example 20> The conditions for producing the surface layer were changed to those shown in Table 30, the conditions for producing the photoconductive layer were changed to several conditions shown in Table 27, and other conditions were the same as those in Example 5. A plurality of drums shown in Table 34 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 5,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained in the same manner 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 forming the IR absorbing 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,
In each case, similarly to Example 6, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 24> The conditions for forming the IR absorption 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. Under the same conditions as in No. 6, a plurality of drums shown in Table 39 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 6,
In each case, similarly to Example 6, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 23> 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 27 to prepare the surface layer. Under the conditions shown in Table 28, a plurality of drums shown in Table 40 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 6,
In each case, similarly to Example 6, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 24> The conditions for forming the IR absorbing 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. Under the conditions shown in Table 30, a plurality of drums shown in Table 41 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 6,
In each case, similarly to Example 6, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 25> A plurality of drums shown in Table 43 were prepared under the same conditions as in Example 7 except that the conditions for forming the adhesive layer were changed to several conditions shown in Table 42.

As a result of subjecting these drums to the same evaluation as in Example 7,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 7.

<Example 26> The conditions for forming the adhesion 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 otherwise the same as Example 7. Under the conditions described above, a plurality of drums shown in Table 45 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 7,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 7.

Example 27 The adhesion layer preparation conditions were changed to several conditions shown in Table 44, the photoconductive layer preparation conditions were changed to several conditions shown in Table 27, and the surface layer preparation conditions were changed to 28th. A plurality of drums shown in Table 46 were prepared under the conditions shown in the table.

As a result of subjecting these drums to the same evaluation as in Example 7,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 7.

<Example 28> The conditions for producing the adhesion layer were changed to several conditions shown in Table 44, the conditions for producing the photoconductive layer were changed to several conditions shown in Table 27, and the conditions for producing the surface layer were changed to No. 30. A plurality of drums shown in Table 47 were prepared under the conditions shown in the table.

As a result of subjecting these drums to the same evaluation as in Example 7,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 7.

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 absorbing 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 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 30> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 49, the conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 38, and other conditions were carried out. 50th under the same conditions as in Example 8
A plurality of drums shown in the table were prepared.

As a result of subjecting these drums to the same evaluation as in Example 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 31> The conditions for producing the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for producing the IR absorption layer were changed to several conditions shown in Tables 35 and 38, and the surface layer was produced. Under the conditions shown in Table 28,
A plurality of drums shown in Table 52 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 32> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 38, and the surface layer was formed. Under the conditions shown in Table 30,
A plurality of drums shown in Table 53 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<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,
In each case, similarly to Example 9, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 34> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 56, and the conditions for forming the adhesion layer were changed to several conditions shown in Tables 44 and 57. A plurality of drums shown in Table 58 was prepared under the same conditions as in No. 9.

As a result of subjecting these drums to the same evaluation as in Example 9,
In each case, similarly to Example 9, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<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 adhesion layer were changed to several conditions shown in Tables 44 and 57, and the conditions for forming the surface layer were changed. Under the conditions shown in Table 28,
59 A plurality of drums shown in the table were prepared.

As a result of subjecting these drums to the same evaluation as in Example 9,
In each case, similarly to Example 9, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 36> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 24, and the conditions for forming the adhesion layer were changed to several conditions shown in Tables 44 and 57 to prepare the surface layer. Under the conditions shown in Table 30,
A plurality of drums shown in Table 60 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 9,
In each case, similarly to Example 9, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<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.

As a result of subjecting these drums to the same evaluation as in Example 10,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 10.

<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 otherwise, Example 10 was used. A plurality of drums shown in Table 65 were prepared under the same conditions as in.

As a result of subjecting these drums to the same evaluation as in Example 10,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 10.

<Example 39> The conditions for producing the charge injection blocking layer were changed to several conditions shown in Table 64, the conditions for producing the photoconductive layer were changed to several conditions shown in Table 66, and the conditions for producing the surface layer were changed. Under the conditions shown in Table 28, 67th
A plurality of drums shown in the table were prepared.

As a result of subjecting these drums to the same evaluation as in Example 10,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 10.

<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. 68th under the conditions shown in Table 30
A plurality of drums shown in the table were prepared.

As a result of subjecting these drums to the same evaluation as in Example 10,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 10.

<Example 41> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 38, and the photoconductive layer A plurality of drums shown in Table 71 were prepared under the conditions shown in Table 69, the conditions for forming the surface layer shown in Table 70, and the conditions shown in Table 69.

As a result of subjecting these drums to the same evaluation as in Example 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 42> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 38, and the photoconductive layer A plurality of drums shown in Table 73 were prepared under the conditions shown in Table 72 and the conditions shown in Table 70 for the preparation of the surface layer.

As a result of subjecting these drums to the same evaluation as in Example 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 43> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 38, and the photoconductive layer A plurality of drums shown in Table 74 were prepared under the conditions shown in Table 69, the conditions for forming the surface layer shown in Table 28, and the conditions shown in Table 69.

As a result of subjecting these drums to the same evaluation as in Example 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 44> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 38, and the photoconductive layer A plurality of drums shown in Table 75 were prepared under the conditions shown in Table 72 and the conditions for forming the surface layer shown in Table 28.

As a result of subjecting these drums to the same evaluation as in Example 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 45> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 38, and the photoconductive layer A plurality of drums shown in Table 76 were prepared under the conditions shown in Table 69 and the conditions shown in Table 30 for the preparation of the surface layer.

As a result of subjecting these drums to the same evaluation as in Example 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 46> The conditions for forming the charge injection blocking layer were changed to several conditions shown in Table 51, the conditions for forming the IR absorption layer were changed to several conditions shown in Tables 35 and 38, and the photoconductive layer A plurality of drums shown in Table 77 were prepared under the conditions shown in Table 72 and the conditions for forming the surface layer shown in Table 30.

As a result of subjecting these drums to the same evaluation as in Example 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 47> The conditions for forming the charge injection blocking layer and the photoconductive layer were set to those shown in Table 78, and a plurality of drums were prepared for forming the surface layer shown in Table 79.

As a result of subjecting these drums to the same evaluation as in Example 4,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 4.

<Example 48> The conditions for forming the IR absorption layer, the charge injection blocking layer, and the photoconductive layer were set to 80th.
Under the conditions shown in the table, a plurality of drums whose surface layer preparation conditions are shown in Table 81 were prepared.

As a result of subjecting these drums to the same evaluation as in Example 8,
In each case, similarly to Example 8, a drum sufficiently satisfying the electrophotographic characteristics was obtained.

<Example 49> The adhesion layer, the IR absorption layer, the charge injection blocking layer, and the photoconductive layer were formed under the conditions shown in Table 82, and the surface layer was formed under the condition 83.
A plurality of drums shown in the table were prepared.

As a result of subjecting these drums to the same evaluation as in Example 10,
In each case, a drum sufficiently satisfying the electrophotographic characteristics was obtained as in Example 10.

<Example 50> A drum was produced in the same manner as in Example 1 under the production conditions shown in Table 84 for the charge injection blocking layer, the photoconductive layer, the intermediate layer and the surface layer, and the same evaluation was performed. As in Example 1, a drum with very good electrophotographic properties was obtained.

<Example 51> A cylinder subjected to mirror surface processing is further subjected to lathe processing with a sword bite having various angles, and a plurality of cylinders having a sectional shape as shown in Fig. 3 and various sectional patterns as shown in Table 85 are provided. I prepared a book. The cylinders were sequentially set in the manufacturing apparatus shown in FIG. 2 and subjected to drum making under the same making conditions as in Example 1. The produced drums were evaluated in the same manner as in Example 1, and as a result, the same drums as in Example 1 were obtained, which satisfied the electrophotographic characteristics.

<Embodiment 52> The surface of a mirror-finished cylinder is subjected to a so-called surface dimple treatment in which the surface of the cylinder is exposed to the dropping base of a large number of bearing balls to produce innumerable dents. A plurality of cylinders having a cross-sectional shape like this and 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 making under the same making conditions as in Example 1. The produced drums were evaluated in the same manner as in Example 1, and as a result, the same drums as in Example 1 were obtained, which satisfied the electrophotographic characteristics.

[Outline of Effects of the Invention] The light-receiving member of the present invention has a lower surface layer made of non-BN (H, X) having a four-coordination structure, and a non-layer having a three-coordination structure and a four-coordination structure mixed therein. By providing a two-layered surface protective layer with an upper surface layer made of BN (H, X) and containing a valence electron control agent in the surface protective layer, excellent moisture resistance and continuous repeated use are obtained. When the photoreceptive member of the present invention is applied as an electrophotographic image forming member, there is no effect of residual potential, and the characteristics, electrical pressure resistance, use environment characteristics, durability, etc. The electrical characteristics are stable, and in particular, there are no image defects and image deletion, and the cleaning property is excellent.

[Brief description of drawings]

1 (A) to (I) are diagrams schematically showing some of the typical examples of the layer structure of the light receiving member of the present invention, and FIG. 2 is for manufacturing the light receiving member of the present invention. FIG. 3 is a schematic explanatory view of a manufacturing device by a glow discharge method, which is an example of the device of FIG. Third
FIG. 4 and FIG. 4 are views showing examples of the sectional shape of the support of the light receiving member of the present invention. 100 ... Photoreceptive member, 101 ... Support, 102 ... Photoconductive layer, 103 ... Surface protective layer, 103 '... Lower surface layer, 103 ″
...... Upper surface layer, 104 …… Charge injection blocking layer, 105 …… Long wavelength light absorption layer, 106 …… Adhesion layer, 107 …… Free surface, 108 ・ ・ ・
... Middle layer, 201 ... Reaction chamber, 202-206, 241,247 ... Gas cylinder, 207-211,242,248 ... Mass flow controller, 212-216,243,249 ... Inflow valve 217-221,24
4,250 ... Outflow valve, 222-226,245,251 ... Valve, 227-231,246,252 ... 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

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yasushi Fujioka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP 62-156666 (JP, A) JP 62 -151857 (JP, A) JP-A-60-225852 (JP, A) JP-A-60-61760 (JP, A)

Claims (6)

[Claims] 1. A support, a photoconductive layer composed of an amorphous material having a silicon atom as a base material and at least one of a hydrogen atom and a halogen atom on the support, and a surface protective layer. In a light receiving member comprising a light receiving layer having at least, the surface protective layer,
A lower surface layer composed of a non-single crystalline material containing only tetracoordinated boron nitride, and a non-single crystal containing a mixture of tetracoordinated boron nitride and tricoordinated boron nitride It is composed of an upper surface layer composed of quality material,
And a light-receiving member containing Si, Sn, Ge or Zn as a valence electron control agent. 2. The light receiving member according to claim 1, wherein the light receiving layer has a multi-layered structure of three or more layers. 3. The light receiving member according to claim 2, 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 absorbing 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 protective layer.