JPH0766195B2 - 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 has a high Vickers hardness and is free from pollution. From the viewpoint of few problems, for example, JP-A-54-
Amorphous materials containing silicon atoms as a base material and containing at least one of hydrogen atoms and / or halogen atoms (hereinafter referred to as "a-Si (H, X)", as disclosed in JP-A-86341 and JP-A-56-83746. The light receiving member is noted.

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, amorphous materials containing boron phosphide (hereinafter referred to as "a-BP").
It is written as. ) Is known to be used. (See JP-A-60-61760) However, when the thin film composed of the a-BP is used as a surface protective layer, various mechanical damages such as contact with a cleaning blade are prevented, Further, it is particularly effective in preventing alteration of the surface of the light receiving member due to ozone and ions generated by corona discharge during charging, but the light receiving member using the surface protective layer composed of the a-BP is Insufficient electrophotographic characteristics such as darkness and dark decay, and when an image is formed using such a light receiving member, there is a problem that ghosts appear on the image and image quality deteriorates. .

[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 present inventors have solved the above-mentioned problems relating to the surface protective layer in the light-receiving member used for the electrophotographic photoreceptor and the like, and have conducted extensive studies to achieve the above-mentioned object of the present invention. Non-single crystalline boron phosphide containing at least one of an atom or a halogen atom (hereinafter, referred to as "Non-BP
(H, X) ”. It was found that the above problems can be solved by using a thin film as the surface protective layer.

That is, when a thin film composed of Non-BP (H, X) is used as a surface protective layer of a light receiving member for an electrophotographic photosensitive member, a hydrogen atom (H) contained in a non-single crystalline boron phosphide or At least one of the halogen atoms (X) compensates for dangling bonds of the non-single crystalline boron phosphide, and a surface protective film having very few defects can be obtained. Further, by containing at least one of a hydrogen atom or a halogen atom in the non-single crystalline boron phosphide, the effective coordination number of each atom constituting the non-single crystalline boron phosphide thin film is reduced, Since the flexibility of the thin film is increased, the surface protection layer using the thin film reduces the defects of the film and also improves the adhesion with other layers provided under the layer.

Therefore, the photoreceptive member for an electrophotographic photoreceptor having a surface protective layer composed of Non-BP (H, X) has high charging ability, little dark decay, high sensitivity, no image deletion, etc. It is possible to obtain an electrophotographic photosensitive member having excellent various properties, high mechanical strength, and good environmental resistance.

Further, the present inventors have further studied the case of using the surface protective layer composed of the above-mentioned Non-BP (H, X), and found that the non-BP (H, X) has valence electron control. It has been found that the inclusion of the agent prevents the accumulation of electric charges in the surface protective layer after image exposure, and provides a light-receiving member in which image deletion and residual potential are not generated.

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. A photoconductive layer composed of an amorphous material containing either one, an amorphous silicon or polycrystalline silicon intermediate layer containing carbon atoms on the photoconductive layer, and a hydrogen atom or a halogen atom on the intermediate layer. Amorphous boron phosphide or polycrystal containing at least one and at least one atom selected from the group consisting of silicon atom, carbon atom, sulfur atom, selenium atom, beryllium atom, magnesium atom, zinc atom, cadmium atom and mercury atom. Characterized by having a light-receptive layer with a surface protective layer composed of a boron phosphide or a mixture thereof. A light-receiving member, in.

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. A typical example of the layer structure of the light-receiving member of the present invention will be described below for electrophotography, but 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 the surface protective layer 103 are provided in this order, and the surface protective layer 103 has a free surface 107.

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, an adhesion layer 106, a photoconductive layer 102, and a surface protective layer 103 are provided in this order on a support 101. . First
In the example shown in (I), the charge injection blocking layer 1 is formed on the support 101.
04, the photoconductive layer 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, scattering, or the like, or the surface is laminated with the metal and the surface thereof is formed. Imparts a thin electrical property to. 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, from the viewpoint of mechanical strength and the like in terms of production and handling of the support, 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.
4 is a layer provided to prevent electrons from being injected into the photoconductive layer 102 from the support side when the photoconductive layer 102 is subjected to a charging treatment, and the charge injection blocking layer 104 is hydrogen. , Or polycrystalline silicon (hereinafter “poly-Si (H, X)”)
I call it. ), Or so-called non-single crystal silicon containing both (hereinafter referred to as “Non-Si (H, X)”).
[Note that what is commonly called microcrystalline silicon is classified into a-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, optimally
It is desirable to set the concentration to 1 × 10 ^{2 to} 5 × 10 ³ atomic ppm.

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, which is particularly preferable when it is composed of poly-Si (H, X). Is 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. The long-wavelength light absorption layer 105 efficiently absorbs the long-wavelength light that could not be completely 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 is revealed. It has a function of remarkably preventing the discharge. And Ge contained in the long wavelength light absorption layer 105
The amount of atoms or the amount of Sn atoms or their sum is 1 to 10
⁶ atomic ppm, preferably 1 × 10 ^{2 to} 9 × 10 ⁵ atomic pp
m, and more preferably 5 × 10 ² to 8 × 10 ⁵ atomic ppm. The amount of hydrogen atoms or halogen atoms contained in the long wavelength light absorption layer 105 is preferably 1 ×.
It is desirable to set 10 ^{3 to} 3 × 10 ⁵ atomic ppm, especially po
In the case of ly-Si (Ge, Sn) (H, X), it is preferably 1 × 10 ³ to 2
× and ^{10 5 atomic ppm, a-Si} (Ge, Sn) (H, X) it is desirable that the case of the preferably at ^{1 × 10 4 ~6 × 10 5} atomic ppm.

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 and 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.
ppm It is desirable to set it to 100 to 4 × 10 ⁵ atomic ppm. Further, the amount of hydrogen atoms or halogen atoms contained in the adhesion layer 106 or the sum thereof is preferably
10 to 7 × 10 ⁵ atomic ppm, especially poly-Si (O, C, N)
In the case of (H, X), 10 to 2 × 10 ⁵ atomic ppm, a-Si (O,
In the case of C, N) (H, X), it is desirable to set the concentration to 1 × 10 ^{3 to} 7 × 10 ⁵ 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
There are various methods for forming the layer composed of (H, X), and the following method can be given as an example.

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 It is desirable to be 5 to 30 atomic%. Further, the purpose of incorporating a Group III 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 1 × 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 free surface 107. And the surface protection layer 1
03 is various characteristics required for the light receiving member, that is, moisture resistance,
Continuous repeated use characteristics, electrical pressure resistance, usage environment characteristics,
And to improve durability, etc., in particular, it has a function of preventing deterioration by ions and ozone caused by mechanical damage and corona discharge on the surface of the light receiving member, and has excellent electrophotographic characteristics such as charging ability and dark decay, It has a function of effectively preventing image deletion and residual potential generation during image formation.

The surface protective layer 103 of the photoreceptive member of the present invention which becomes fragile is a non-single crystalline boron phosphide [“Non-BP
(H, X) ”, that is, amorphous boron phosphide [hereinafter,
Indicated as "a-BP (H, X)". ] Or polycrystalline boron phosphide [hereinafter referred to as “poly-BP (H, X)”. ] Or a mixture of both.

As the valence electron control agent contained in the surface protective layer 103 of the present invention, a dopant which functions as a donor in the case of positive charging and a dopant which functions as an acceptor in the case of negative charging are used. Specifically, as an example of the former, silicon atom (Si), germanium atom (G
e), sulfur atom (S), selenium atom (Se), or a mixture of two or more of them. Examples of the latter include beryllium atom (Be), magnesium atom (Mg) zinc atom (Zn). ), Cadmium atom (Cd), mercury atom (Hg), carbon atom (C), silicon atom (Si), germanium atom (Ge), or a mixture of two or more of these.

The amount of these valence electron control agents to be contained in the surface protective layer is usually 1000 atomic ppm or less, preferably 700 atomic ppm or less, and most preferably 500 atomic ppm.
The following is preferable. Further, when the composition ratio of Non-BP (H, X) that constitutes the surface protective layer 103 is represented by (B _x P _1-x ) _1-y (H, X) _y , the following conditions are satisfied. Is desirable.

For x; 0.1 ≦ x ≦ 0.9, preferably 0.2 ≦ x ≦ 0.8, optimally 0.3 ≦
For x ≦ 0.7 y; 0.001 ≦ y ≦ 0.4, preferably 0.005 ≦ y ≦ 0.3, optimally
0.006 ≦ y ≦ 0.2 In the light receiving member of the present invention, the layer thickness of the surface protective layer 103 is also one of the important factors for efficiently achieving the object of the present invention, and is appropriately selected according to the desired object. Although it is determined, it is necessary to make mutual and organic determinations depending on the amount of constituent atoms contained in the surface protective layer or the characteristics 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 0.003 to 30μ, more preferably 0.
004 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 10
The amount of carbon atoms contained in 8 is preferably 20 to 90a
tomic%, more preferably 30-85 atomic%, optimally 40
It is desirable to set it to 80 atomic%. Also, the intermediate layer 108
The amount of hydrogen atom (H), the amount of halogen atom (X), and the amount of hydrogen atom + halogen atom (H + X) contained therein 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 amorphous materials constituting the light receiving member of the present invention are all glow discharge methods (low frequency CVD, high frequency CVD or microwave CV
AC discharge CVD such as D, or DC discharge CVD, etc.), sputtering method, vacuum deposition method, ion plating method, light
It can be formed by various thin film deposition methods such as a CVD method and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load of capital investment, manufacturing scale, and characteristics desired for the 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
In order to form a surface protective layer composed of Non-BP (H, X), basically, a source gas for supplying P that can supply phosphorus atoms (P) and a boron atom (B) are supplied. The raw material gas for supplying B, the raw material gas for introducing a hydrogen atom (H) and / or the halogen atom (X), and the raw material gas for introducing a valence electron control agent are placed in a deposition chamber in which the inside pressure can be reduced. Introduce,
A glow discharge is generated in the deposition chamber to form a layer composed of Non-BP (H, X).

As the raw material gas for supplying B, B ₂ H ₆ , B ₄ H ₁₀ , B
_{5 H 9, B 6 H 12} , BF 3, a compound capable of or gasified gas state such as BCl ₃ and the like.

Further, as the raw material gas for supplying P, PH ₃ , P ₂ H ₄ , P
Examples thereof include compounds in a gas state or gasifiable such as F ₃ , PCl ₃ , PF ₅ , and PCl ₅ .

Further, among the raw material gases for introducing the valence electron control agent, as the raw material gas for introducing the dopant functioning as a donor, SiH ₄ , Si ₂ H ₆ , SiF ₄ for introducing a silicon atom (Si), and a germanium atom ( Ge) GeH for introducing _4, GeF _4, SF ₄ sulfur atoms (S) for _{introducing, SF 6, SCl 2, S} 2 Br 2, H 2 S, SeF 4 selenium atoms (Se) for introducing, SeF ₆ , SeH ₂ or the like in a gas state or a gasifiable compound, and as a raw material gas for introducing a dopant functioning as an acceptor, Be (CH ₃ ) ₂ for introducing beryllium atom (Be), Be (C ₂ H _{2 5} ) ₂ , MgCH ₃ Cl for introducing magnesium atom (Mg), Zn (CH ₂ ) ₂ , Zn (C ₂ H ₅ ) ₂ for introducing zinc atom (Zn), Cd (Cd) for introducing cadmium atom (Cd) _{CH 3) 2, Cd (C} 2 H 5) 2, Cd (C 3 H 7) 2, mercury atoms (Hg)
Hg for introduction, Hg (CH ₃ ) ₂ , CH ₄ for introduction of carbon atom (C), C
₂ H ₆ , C ₂ H ₄ , C ₂ H ₂ , SiH ₄ , Si ₂ for introducing silicon atoms (Si)
H ₄ , SiF ₄ , GeH ₄ for introducing germanium atom (Ge), GiF ₄
Compounds in a gas state or gasifiable such as

Further, in order to form a Non-BP (H, X) layer containing a valence electron control agent by a sputtering method, a B target is used as a target, and the P supply source gas and the source for introducing the valence electron control agent are used. Gas and Ar gas are introduced into the deposition chamber to form plasma, and the B target is sputtered, or a BP target is used as a target to introduce the B and P supply source gases and the valence electron control agent. The raw material gas and Ar gas are introduced into the deposition chamber to form plasma, and the BP target is sputtered.

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 H _{10 and} other gas-state or gasifiable silicon hydrides (silanes) can be mentioned. In particular, SiH ₄ , Si ₂ H ₆ is preferable in terms of easiness of layer forming work and good Si supply efficiency. Is preferred.

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,
Iodine halogen gas, BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃ ,
Interhalogen compounds such as IF ₇ , IC1, IBr, and SiF ₄ , Si ₂
Examples thereof include silicon halides such as F ₆ , SiCl 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, HC1, HBr and HI, SiH ₄ , Si
_{2 H 6, Si 3 H 8} , Si 4 H 10 hydride such as silicon or SiH ₂ F _{2,,
SiH 2 I 2, SiH 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., use these material gases In that case, it is effective because the content of hydrogen atoms (H), which is extremely effective in controlling the electrical or photoelectric characteristics, can be easily controlled. 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
It is possible to use germanium hydride in a gas state or gasifiable such as ₇ H ₁₆ , Ge ₈ H ₁₈ , and Ge ₉ H ₂₀ . In particular, in terms of ease of handling during layer creation work and good Ge supply efficiency, Ge
H 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
This is carried out by using two targets of germanium or a target of silicon and germanium, and sputtering these in a 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 raw material gas for supplying halogen atoms, the above-mentioned halides or silicon compounds containing halogen are mentioned as effective ones, but in addition, hydrogen halides such as HF, HC1, HBr, and HI, SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , S
iH ₂ Br ₂ , SiHBr ₃ , etc., halogen-substituted silicon hydride, and
GeHF ₃ , GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ , GeH ₃ Cl, GeH
_{Br 3, GeH 2 Br 2,} GeH 3 Br, GeHI 3, GeH 2 I 2, GeH 3 I hydride germanium halide such _{as, GeF 4, GeCl 4, GeBr} 4, Ge
Gaseous or gasifiable substances such as germanium halides such as I ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , 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 substance that can be the source gas for supplying the tin atom (Sn) include tin hydride (SnH ₄ ), SnF ₂ , SnF ₄ , SnCl ₂ , and SnC.
l _4, SnBr _2, SnBr _4, SnI _2, those can be used which can be SnI or gasified gas state such as tin halide, such as _4,
The use of tin halide is particularly effective because a layer composed of a-Si containing halogen atoms can be formed on a predetermined support. Above all, from the viewpoint of ease of handling during layer creation work, good Sn supply efficiency, etc.,
SnCl ₄ is preferred.

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 ), 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 N), 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 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, 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. 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. The atoms and the source gas can also be mixed or used in the 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 oxygen atoms (O) 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 ), gaseous or gasifiable nitrogen such as hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen compounds such as boron nitride and azide be able to. In addition to this, in addition to the introduction of nitrogen atoms,
Nitrogen halide compounds such as nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F ₄ N) can be mentioned from the viewpoint of introducing a halogen atom.

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
This may be performed by using a wafer containing N ₄ mixed therein as a target and sputtering these 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 source gas for introducing oxygen atoms, the source gas for introducing nitrogen atoms in the source gas shown in the example of the 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 12} , B 6 H 14 borohydride such _{as, BF 3, BCl 3, BBr} 3
And the like. Besides this, AlC1 ₃ , G
Other examples include aC1 ₃ , Ga (CH ₃ ) ₂ , InC1 ₃ and TlC1 ₃ .

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 , P
Examples thereof include phosphorus halides such as Cl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsC 1 ₃ , AsBr ₃ , AsF ₅ , Sb
_{H 3, SbH 3, SbF 5} , SbC1 3, SbC1 5, BiH 3, BiC1 3, mention may be made of BiBr ₅ like as a valid starting material for the group V atoms introduced.

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, when the surface protection layer made of Non-BP (N, X) containing a valence electron control agent is formed by the high frequency (13.56MHz) plasma CVD method, the gas pressure in the deposition chamber is usually 10 ^-2. ~
The pressure is 10 Torr, more preferably 5 × 10 ^{−2 to 2} Torr, most preferably 0.1 to 1 Torr. The support temperature is usually 50.
~ 700 ℃, especially Nom-BP (N, X) layer 50 ~ 400 ℃, poly-BP (H, X) layer 200 ~ 7
Set to 00 ° C. Further, the discharge power is usually 0.01 to 5 W / cm ² , and more preferably 0.02 to ² W / cm ² . Furthermore, the gas flow ratio of the B supply source gas and the P supply source gas is such that B / P is 1
100-100 / 1, more preferably 1 / 50-50 / 1, optimally 1/3
Try to be between 0 and 30/1.

When the surface protection layer made of Non-BP (H, X) containing a valence electron control agent is formed by the microwave (2.45 GHz) plasma CVD method, the gas pressure in the deposition chamber is usually 10 ^{-4 to 2} Torr.
r, more preferably 5 × 10 ^{−4 to} 1.0 Torr, and the discharge power is usually 0.1 to 50 W / cm ² , more preferably 0.2 to 30 W / 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, when the surface protective layer made of Non-BP (H, X) containing a valence electron control agent 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} 0.77 Torr, discharge power 0.01 to 10 W / c
m 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.

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, and 241 in the figure are sealed with the raw material gas for forming the layers of the present invention. As an example, for example, 202 is SiH ₄ gas. (Purity 99.999%) cylinder, 203 is B ₂ H ₆ diluted with H ₂
Gas (purity 99.999%, hereinafter abbreviated as B ₂ H ₆ / H ₂ ) cylinder, 20
4 is NO gas (purity 99.5%) cylinder, 205 was diluted with H ₂ .
B ₂ H ₆ gas (99.999% purity, less B ₂ abbreviated as H ₆ / H ₂₎ cylinder, 206 H ₂ S gas diluted with H ₂ (purity 99.999%, or less
H ₂ abbreviated as S / H ₂₎ cylinder, 241 H ₂ PH ₃ gas (99.999% purity diluted by the following PH ₃ / H ₂ abbreviated) is cylinder.

A gas cylinder 2 is used to allow these gases to flow into the reaction chamber 201.
Check that the valves 02 to 206 and the leak valve 235 are closed, and check the inflow valves 212 to 216 and the outflow valve 217.
~ 221 and auxiliary valves 232 to 233 are confirmed to be open, the main valve 234 is first opened to exhaust the reaction chamber 201 and the gas pipe. Next, the reading of the vacuum gauge 236 is about 5 × 10 ^-6 Torr
Auxiliary valve 232-233, outflow valve 217
Close ~ 221.

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 gauge 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 the SiH ₄ gas flow rate, the B ₂ H ₆ / H ₂ gas flow rate, and the 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 confirming 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 electric power to cause glow discharge in the reaction chamber 201 and the base. Form a first layer on the 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 created as described above, the outflow valves 217-221 are closed and the auxiliary valve 232 is closed.
~ 233 is opened and the main valve 234 is fully opened to evacuate the system to a high vacuum once, and then B ₂ H ₆ / H ₂ gas and PH ₃ / H are operated by the same valve operation as in forming the first layer. ₂ Gas and gas containing valence electron control agent component, in the example of FIG.
H ₂ S / H ₂ gas of 6 is flowed into the reaction chamber 101 at a desired flow rate ratio,
It is done by causing a glow discharge according to the desired conditions.

When changing the amount of hydrogen atoms contained in the second layer, for example, H ₂ gas is added to the above gas, and the flow rate of H ₂ gas introduced into the reaction chamber 101 can be arbitrarily set as desired. Can be controlled as desired by changing to.

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

Needless to say, all the outflows other than the gas necessary for forming the respective layers are closed, and when the respective layers are formed, the gas used for forming the front layer is the reaction chamber 101 inside the outflow valve 217-. In order to avoid remaining in the pipe from 221 to the inside of the reaction chamber 101, the outflow valves 217 to 221 are closed, the auxiliary valves 232 to 233 are opened, the main valve 234 is fully opened, and the system is once evacuated to a high vacuum. Perform operations as needed.

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 according to the preparation conditions shown in Table 1.

The light receiving member (hereinafter referred to as a drum) is set in an electrophotographic apparatus to check the electrophotographic characteristics such as initial charging ability, residual potential and ghost under various conditions.
We investigated the deterioration of charging ability, surface scraping, and increase in image defects after the endurance of 10,000 sheets. 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 can be seen from Table 2, remarkable advantages were recognized particularly in the initial chargeability, ghost, image defects, surface abrasion, withstand voltage, and scratch resistance.

<Example 2> In the same manner as in Example 1 except that the conditions for forming the surface layer were changed to several conditions shown in Table 3, the amount of H or F in the surface layer was different, and the valence electron control agent was used. A plurality of drums including the above 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.

<Example 3> In the same manner as in Example 1 except that the preparation conditions of the surface layer were changed to several conditions shown in Table 5, the B amount and the P amount in the surface layer were different, and the valence electron control agent was used. A plurality of drums containing was prepared and evaluated in the same manner as in Example 1.

The results are shown in Table 6.

As shown in Table 6, the same characteristics as in Example 1 were obtained.

<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 formed under the conditions shown in Tables 7 (a) and 7 (b), respectively. An evaluation was made.

The results are shown in Table 8.

As shown in Table 8, 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 for the surface layers in the same manner as in Example 4, and the same evaluations as in Example 1 were performed.

The results are shown in Table 9.

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

<Example 6> A long wavelength light absorbing layer (hereinafter referred to as "IR absorbing layer"), a photoconductive layer, and a surface layer were respectively prepared under the conditions shown in Table 10 to prepare a drum in the same manner as in Example 1. 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 A drum was produced in the same manner as in Example 1 under the production conditions shown in Table 12 for the adhesive layer, the photoconductive layer, and the surface layer, 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> An IR absorption layer, a charge injection blocking layer, a photoconductive layer, and a surface layer were formed into a drum in the same manner as in Example 1 under the production conditions shown in Table 14, and evaluated in the same manner as in Example 6. I went.

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 preparation conditions shown in Table 16, and the same evaluation was performed.

The results are shown in Table 17.

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

<Example 10> A drum was prepared in the same manner as in Example 1 except that the adhesion layer, the IR absorption layer, the charge injection blocking layer, the photoconductive layer, and the surface layer were formed under the conditions shown in Table 18, respectively. The same evaluation as was done.

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 12,
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,
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 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.

<Embodiment 51> Mirror-finished cylinders are further subjected to lathe processing with a sword bite having various angles, and a plurality of cylinders having various cross-sectional patterns as shown in Table 85 are formed in a judgment shape as shown in FIG. 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 cylinder that has been mirror-finished 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 various cross-sectional patterns as shown in Table 86 with the judgment shape as described above 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 is a hydrogen atom or, by providing a surface protective layer composed of Non-BP containing at least one of a halogen atom, the mechanical surface of the light receiving member. In addition to preventing damage, the electrophotographic characteristics such as charging ability and dark decay are excellent, and when the photoreceptor of the present invention is applied as an electrophotographic image forming member, the influence of residual potential is The electrical characteristics are stable, and the image obtained by using it is excellent without the occurrence of ghosts and image defects.

[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, 104 ... Charge injection blocking layer, 105
...... Long wavelength light absorption layer, 106 ...... adhesion layer, 107 ...... free surface, 108 …… intermediate layer, 201 …… reaction chamber, 202 to 206 …… gas cylinder, 207 to 211 …… mass flow controller, 212 〜 216
...... Inflow valve, 217-221 …… Outflow valve, 222-226…
… Valve, 227-231 …… Pressure regulator, 232,233 …… Auxiliary valve, 234 …… Main valve, 235 …… Leak valve,
236 ... Vacuum gauge, 237 ... Base cylinder, 238 ... Heating 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-A-60-225164 (JP, A) JP-A-60 -227262 (JP, A) JP-A-60-61760 (JP, A)

Claims (4)

[Claims] 1. A support, a photoconductive layer comprising a silicon atom as a base material and an amorphous material containing at least one of a hydrogen atom and a halogen atom on the support, and the photoconductive layer. Amorphous silicon or polycrystalline silicon intermediate layer containing carbon atoms on the layer, and at least one of hydrogen atoms or halogen atoms on the intermediate layer, and silicon atoms, carbon atoms, sulfur atoms, selenium atoms, beryllium atoms, magnesium Photoreceptor comprising an amorphous boron phosphide or polycrystalline boron phosphide or a mixture thereof containing at least one atom selected from the group consisting of atoms, zinc atoms, cadmium atoms and mercury atoms A light-receiving member having a layer. 2. The light receiving member according to claim 1, wherein the light receiving layer has a charge injection blocking layer. 3. The light receiving member according to claim 1, wherein the light receiving layer has a long wavelength light absorbing layer. 4. The light-receiving member according to claim 1, wherein the light-receiving layer has an adhesion layer having a function of improving adhesion.