JP2637425B2 - Light receiving member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to electromagnetic waves such as light (here, light in a broad sense, meaning ultraviolet light, visible light, infrared light, X-rays, γ-rays, etc.). To a light receiving member that is sensitive to light.

(Prior art)

In the field of image formation, the photoconductive material constituting the light receiving layer of the light receiving member has a high sensitivity, a high SN ratio (photocurrent (Ip) / dark current (Id)), and a high spectral response to the electromagnetic wave to be irradiated. It is required to have characteristics such as having an appropriate absorption spectrum characteristic, quick light response and a desired dark resistance value, and being harmless to a human body during use. In particular, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used in an office as an office machine, the above-described non-pollutability during use is important.

Amorphous silicon (hereinafter referred to as A-Si) is a photoconductive material that has recently attracted attention based on this point. For example, German Patent Publication Nos. 2746967 and 2855718 disclose electronic materials. FIG. 2 in which application as a photographic light receiving member is described. FIG. 2 is a cross-sectional view schematically showing a layer structure of a conventional electrophotographic light receiving member, wherein 201 is an aluminum-based support, and 202 is A -Photosensitive layer made of Si. Such an electrophotographic light-receiving member is generally made of an aluminum-based support.
201 is heated to 50 ° C to 350 ° C, deposited on the support, thermal CVD
A by a film forming method such as a plasma CVD method, sputtering, etc.
-A photosensitive layer 202 made of Si is formed.

However, in this electrophotographic light receiving member, cracks and peeling may occur in the A-Si photosensitive layer 202 during cooling after film formation because the thermal expansion coefficients of aluminum and A-Si are different by about one digit. It is a problem. In order to solve these problems, JP-A-59-28162 proposes an electrophotographic photosensitive member comprising an aluminum-based support, an intermediate layer containing at least aluminum, and an A-Si photosensitive layer. And by an intermediate layer containing at least aluminum,
The stress generated due to the difference in thermal expansion coefficient between the aluminum-based support and the A-Si photosensitive layer is reduced, and cracks and peeling of the A-Si photosensitive layer are reduced.

[Problems to be solved by the invention]

However, conventional electrophotographic light-receiving members having a light-receiving layer composed of A-Si have electrical, optical and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and use environment characteristics. In terms of the point, and also the stability in light and the durability, the characteristics are individually improved, but there is room for further improvement in measuring the overall characteristics. It is a fact.

For example, in recent years, optical exposure devices, developing devices, transfer devices, and the like in electrophotographic devices have been improved in order to improve image characteristics of electrophotographic devices. Is required. In particular, as a result of the improvement in image resolution, reduction of non-uniformity in fine areas of image density, commonly referred to as "graininess", and reduction of black or white spot image defects, commonly referred to as "pochi" In particular, there has been a demand for a reduction in "pockets" of minute size, which has not been regarded as a problem in the past.

Furthermore, when foreign matter mixed in the electrophotographic apparatus comes into contact with the electrophotographic light receiving member, or when the electrophotographic light receiving member comes into contact with the electrophotographic apparatus main body or the maintenance tool during maintenance of the electrophotographic apparatus. There has been a problem that durability of the electrophotographic light receiving member is impaired due to the occurrence of image defects due to the mechanical pressure of the impact applied for a relatively short time and the peeling of the A-Si film. Further, there is a problem that cracks and peeling occur in the A-Si film due to stress generated due to a difference in the coefficient of thermal expansion between the aluminum-based support and the A-Si film, thereby reducing the yield in productivity.

Therefore, while the characteristics of the A-Si material itself are improved, when designing the light receiving member for electrophotography, the overall structure of the light receiving member for electrophotography is designed so that all the above-mentioned problems are solved. There is a need to make improvements from a strategic point of view.

[Means and actions for solving the problems]

The light-receiving member of the present invention is an aluminum-based support, and a light-receiving member having a multi-layered light-receiving layer exhibiting photoconductivity on the support, wherein the light-receiving layer is a constituent element from the support side. At least aluminum atoms, silicon atoms, hydrogen atoms, halogen atoms, and the periodic rate table II excluding aluminum atoms as atoms for adjusting image quality
A lower portion made of an inorganic material containing at least one selected from the group I atoms, the atoms belonging to Group V of the periodic table excluding nitrogen atoms, and the atoms belonging to Group VI of the periodic table excluding oxygen atoms; Layers and silicon atoms as the parent,
It is composed of a non-single-crystal material containing at least one selected from a hydrogen atom and a halogen atom, and a layer region in contact with the lower layer contains carbon atoms (C), nitrogen atoms (N), and oxygen atoms (O). An upper layer containing at least one type of selected atoms, wherein the lower layer has a content of 5 atomic% of the aluminum atoms in the lower layer by changing at least a hydrogen gas introduction ratio.
And 95% by atom or less, and a portion containing the non-uniform distribution in the layer thickness direction such that the content decreases toward the upper layer. The atom has a portion containing the atom in a non-uniform distribution state in the layer thickness direction such that the content increases toward the upper layer, and the content of the hydrogen atom is 0.01 atom% or more and 70 atom% or less. It is characterized by:

The light receiving member for electrophotography of the present invention designed so as to have the above-mentioned layer constitution can solve all of the above problems, and has extremely excellent electrical properties, optical properties, and photoconductive properties. , Image characteristics, durability and use environment characteristics.

Furthermore, in the lower layer, aluminum atoms (Al),
Inclusion of silicon atoms (Si), especially hydrogen atoms (H), in a non-uniform distribution in the layer thickness direction, improving the injection of charge (photocarrier) between the aluminum-based support and the upper layer. Further, since the structural and structural continuity of the constituent elements of the aluminum-based support and the upper layer is improved, image characteristics such as roughness and spots are improved, halftones are clearly produced, and High-quality images with high resolution can be stably and repeatedly obtained.

Furthermore, image defects occur due to the relatively short-time impact mechanical pressure applied to the electrophotographic light-receiving member, and non-Si
(H, X) Prevents peeling of film and improves durability,
Furthermore, the stress generated due to the difference in the coefficient of thermal expansion between the aluminum-based support and the non-Si (H, X) film is reduced, and the non-Si
Cracks and peeling of the (H, X) film can be prevented, and the yield in productivity can be improved.

In particular, in the present invention, silicon atoms (Si),
Since it is possible to compensate for dangling bonds such as aluminum atoms (Al) and to obtain a more structurally and structurally stable state,
Characteristically, there is a remarkable improvement in image characteristics such as roughness and spots, coupled with the effect of the distribution of silicon atoms (Si), aluminum atoms (Al), and hydrogen atoms (H).

Further, in the present invention, a layer region in contact with the lower layer in the upper layer contains at least one of carbon atoms (C), nitrogen atoms (N), and oxygen atoms (O), thereby forming a layer of the upper layer. The quality is improved, the durability against high voltage is improved, and the adhesion between the upper layer and the lower layer is further improved, so that image defects or non-Si (H,
X) The peeling of the film is prevented and the durability is improved.

Japanese Patent Application Laid-Open No. 59-28162 mentions that aluminum atoms (Al) and silicon atoms (Si) are non-uniformly contained in the layer thickness direction, and that they further contain hydrogen atoms. However, it does not mention how hydrogen atoms are contained, and is clearly distinguished from the present invention.

[Specific description of the invention]

Hereinafter, the electrophotographic light-receiving member of the present invention will be described in detail with reference to the drawings by using specific examples.

FIG. 1 is a schematic diagram schematically illustrating a preferred layer structure of the electrophotographic light-receiving member of the present invention.

The electrophotographic light-receiving member 100 shown in FIG. 1 is composed of AlSiH on an aluminum-based support 101 for an electrophotographic light-receiving member, and the aluminum atom (Al)
Layer 103 having a portion containing silicon, silicon atoms (si) and hydrogen atoms (H) in a non-uniform distribution in the thickness direction.
And at least one of carbon atoms (C), nitrogen atoms (N) and oxygen atoms (O) in a layer region which is made of Non-Si (H, X) and is in contact with the lower layer. And a light receiving layer 102 having a layer configuration composed of an upper layer 104. Top layer 104 has a free surface 105.

Support Aluminum-based support 101 used in the present invention
, An aluminum alloy is used. In the aluminum alloy of the present invention, there is no particular limitation on the alloy components including the base aluminum, and the types and compositions of the components can be arbitrarily selected. Therefore, the aluminum alloy of the present invention is standardized or registered as a wrought material, for casting, die casting, etc. according to Japanese Industrial Standards (JIS), AA Standard, BS Standard, DIN Standard, International Alloy Registration, etc. Aluminum, Al-Cu, Al-Mn, Al
Alloys with compositions such as -Si, Al-Mg, Al-Mg-Si, Al-Zn-Mg, Al-Cu-Mg (duralumin, super duralumin, etc.), Al-Cu-Si ( Lautal), Al-Cu-Ni-Mg (Y
Alloy, RR alloy, etc.), aluminum powder sintered compact (SAP), etc.

Incidentally, the specific composition of the aluminum alloy of the present invention is illustrated below, but this is merely an example of the present invention, and the present invention is not limited by the following examples.

Examples of the pure aluminum system include, for example, JIS1100 of 1.0% by weight or less of Si and Fe, 0.05 to 0.20% by weight of Cu, 0.05% by weight or less of Mn, 0.10% by weight or less of Zn, and 99.00% by weight or more of Al.

As the Al-Cu-Mg system, for example, JIS2017, Si 0.05-0.
20 wt%, Fe 0.7 wt% or less, Cu 3.5-4.5 wt%, Mn
0.40-1.0 wt%, Mg 0.40-0.8 wt%, Zn 0.25 wt%
Below, 0.10% by weight or less of Cr and the balance of Al are listed.

Examples of the Al-Mn type include, for example, JIS3003, Si 0.6% by weight or less, Fe 0.7% by weight or less, Cu 0.05 to 0.20% by weight, Mn 1.0
To 1.5% by weight, Zn 0.10% by weight or less, and the balance of Al.

Examples of the Al-Si type include, for example, JIS4032 Si 11.0 to 13.5% by weight Fe 1.0% by weight or less, Cu 0.50 to 1.3% by weight, Mg 0.8
To 1.3% by weight, Zn 0.25% by weight or less, Cr 0.10% by weight or less, Ni 0.5 to 1.3% by weight, and the balance of Al.

Examples of the Al-Mg type include, for example, JIS5086, Si 0.40 wt% or less, Fe 0.50 wt% or less, Cu 0.10 wt% or less, Mn 0.20 wt%
To 0.7% by weight, Mg 3.5 to 4.5% by weight, Zn 0.25% by weight or less, Cr 0.05 to 0.25% by weight, Ti 0.15% by weight or less, and the balance of Al.

Furthermore, Si 0.50 wt% or less, Fe 0.25 wt% or less,
Cu 0.04-0.20% by weight, Mn 0.01-1.0% by weight, Mg 0.5-1
0 wt%, Zn 0.03 to 0.25 wt% or less, Cr 0.05 to 0.50 wt%, Ti or Tr 0.05 to 0.20 wt%, 1.0 cc or less per 100 g of H ₂ Al, and the balance of Al.

Further, furthermore, Si 0.12% by weight or less, Fe 0.15% by weight
Below, Mn 0.30% by weight or less, Mg 0.5-5.5% by weight, Zn 0.0
1 to 1.0 wt% or less, Cr 0.20 wt% or less, Zr 0.01 to 0.25
% By weight or less, and the balance of Al.

As the Al-Mg-Si system, for example, JIS6063, Si0.20-0.6
Wt%, Fe 0.35 wt% or less, Cu 0.10 wt% or less, Mn
0.10% by weight or less, Mg 0.45 to 0.9% by weight, Zn 0.10% by weight or less, Cr 0.10% by weight or less, Ti 0.10% by weight or less, and the balance of Al.

Examples of the Al-Zn-Mg type include, for example, JIS7N01, Si 0.30% by weight or less, Fe 0.35% by weight or less, Cu 0.20% by weight or less, Mn
0.20 to 0.7% by weight, Mg 1.0 to 2.0% by weight, Zn 4.0 to 5.0% by weight, Cr 0.30% by weight or less, Ti 0.20% by weight or less, Zr 0.2
5% by weight or less, V 0.10% by weight or less, and the balance of Al.

To select the composition of the aluminum alloy in the present invention, as properties according to the purpose of use, for example, mechanical strength,
It may be appropriately selected in consideration of corrosion resistance, workability, heat resistance, dimensional accuracy, etc. For example, when precision machining involves mirror cutting, magnesium and / or copper coexist in the aluminum alloy. By doing so, the free-cutting property of the aluminum alloy is improved.

In the present invention, the shape of the aluminum-based support 101 is
It can be in the form of a cylindrical or plate-like endless belt with a smooth or uneven surface, and its thickness is appropriately determined so as to form a desired electrophotographic light-receiving member.
When flexibility as an electrophotographic light-receiving 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 the production and handling of the support and the mechanical strength, it is usually 10
μm or more.

When image recording is performed using coherent light such as laser light, irregularities may be provided on the surface of the aluminum-based support in order to eliminate image defects due to so-called interference fringe patterns appearing in a visible image.

The unevenness provided on the surface of the support is prepared by a known method described in JP-A-60-168156, JP-A-60-178457, JP-A-60-225854 and the like.

Further, as another method for eliminating image defects due to interference fringe patterns when using coherent light such as laser light, a concave-convex shape formed by a plurality of spherical trace depressions may be provided on the surface of the support.

That is, the surface of the support has irregularities finer than the resolving power required for the light receiving member for electrophotography, and the irregularities are caused by a plurality of spherical trace depressions.

The irregularities due to the plurality of spherical trace dents provided on the surface of the support are created by a known method described in JP-A-61-231561.

Lower Layer The lower layer in the present invention is an inorganic material containing at least aluminum atoms (Al), silicon atoms (Si), hydrogen atoms (H), halogen atoms (X) and atoms (Mc) for adjusting image quality as constituent elements. It may be configured and contain atoms (CNOc) for adjusting the durability as necessary.

Aluminum atoms (Al), silicon atoms (Si), and hydrogen atoms (H) contained in the lower layer are uniformly contained in all the layer regions of the lower layer, but their distribution in the layer thickness direction. It has a part where the concentration is uneven. However, in the in-plane direction parallel to the surface of the support, it is necessary that the metal is uniformly distributed and uniformly distributed from the viewpoint of making the characteristics in the in-plane direction uniform.

Halogen atoms (X) contained in the lower layer, atoms for adjusting durability (CNOc), and atoms for adjusting image quality (Mc)
May be contained in the entire layer region of the lower layer in an evenly distributed state, or may be contained in the entire layer region of the lower layer without deviation, but not uniformly in the thickness direction. Some portions may be contained in a state of being uniformly distributed. However, in any case, in the in-plane direction parallel to the surface of the support, it is uniformly contained with uniform distribution,
This is necessary from the viewpoint of achieving uniform characteristics in the in-plane direction.

In one of the preferred embodiments, aluminum atoms (Al) and silicon atoms (S
i) The distribution of hydrogen atoms (H) is as follows: aluminum (Al), silicon (Si), hydrogen (H)
Are distributed continuously and without unevenness, and the distribution concentration of aluminum atoms (Al) in the layer thickness direction decreases from the support side toward the upper layer, and silicon atoms (Si) and hydrogen atoms (H) are changed. Since the distribution density in the layer thickness direction increases from the support side toward the upper layer, the affinity between the aluminum-based support and the lower layer and between the lower layer and the upper layer is excellent.

In the electrophotographic light-receiving member of the present invention, aluminum atoms (Al) contained in the lower layer as described above,
The distribution state of silicon atoms (Si) and hydrogen atoms (H) takes the above-mentioned distribution state in the layer thickness direction, and becomes uniform in the in-plane direction parallel to the surface of the support. Is desirable.

FIGS. 3 to 8 show the aluminum atoms (A) contained in the lower layer of the electrophotographic light-receiving member of the present invention.
l), halogen atom (X), atom for adjusting image quality (M
c) if necessary, the atoms that adjust the durability (C
A typical example of the distribution state of NOc) in the layer thickness direction is shown.

3 to 8, the horizontal axis is the aluminum atom (Al) (hereinafter abbreviated as “atom (Al)”), the halogen atom (X) (hereinafter abbreviated as “atom (X)”), and the durability. Atom (CNOc) (hereinafter abbreviated as “atom (CNOc)”), atom (Mc) (hereinafter “atom (Mc)”) to adjust image quality
And the atom (Al), the atom (X), the atom (CNOc), and the atom (Mc) are collectively abbreviated as “atom (AX)”. However,
The distribution concentration C of atoms (Al), atoms (X), atoms (CNOc), and atoms (Mc) in the layer thickness direction may be the same or different), and the vertical axis indicates the lower layer. Indicates the layer thickness of t _B
The position of the end face of the lower layer on the support side, t _T represents the position of the end face of the lower layer of the upper layer side. That is, the lower layer contained the atoms (AX) is a layer formed toward the t _T side from t _B side.

FIG. 3 shows a first typical example of the distribution of atoms (AX) contained in the lower layer in the thickness direction.

In the example shown in FIG. 3, the distribution concentration C of the atoms contained (AX) is up to the position t _B to the position t ₃₁ takes a constant value the concentration C ₃₁ becomes, leading to the position t _T to the position t ₃₁ reduced from the concentration C ₃₁ linear function manner to form a kind of distribution that the concentration C ₃₂ at position t _T.

In the example shown in Figure 4, the distribution concentration C of the atoms contained (AX) is reduced from the concentration C ₄₁ primary function to up to the position t _T to the position t _B, the concentration C at position t _T A distribution state of ₄₂ is formed.

In the example shown in FIG. 5, the distribution concentration C of the atoms contained (AX) gradually decreases continuously from the concentration C ₅₁ up to the position t _T to the position t _B, the concentration at position t _T forming a kind of distribution becomes C _52.

In the example shown in Figure 6, the distribution concentration C of the atoms contained (AX) takes a constant value to the position t ₆₁ is composed concentration C ₆₁ from the position t _B, to the position t _T to the position t ₆₁ is reduced from the concentration C ₆₂ primary function to form a kind of distribution that the concentration C ₆₃ at position t _T.

Distribution concentration C of the atoms contained (AX) in the example shown in FIG. 7 is to the position t ₇₁ from the position t _B takes a constant value consisting concentration C _71, up to the position t _T to the position t ₇₁ gradually decreases continuously from the concentration C _72, forming a kind of distribution that the concentration C ₇₃ at position t _T.

The distribution density C of the atoms contained (AX) the example shown in FIG. 8, and gradually decreases continuously from the concentration C ₈₁ up to the position t _T to the position t _B, the concentration C at position t _T A distribution state such as ₈₂ is formed.

As described above, some typical examples of the distribution state of the atoms (Al) contained in the lower layer in the layer thickness direction have been described with reference to FIGS. 3 to 8.
Silicon atoms (Si), comprising a hydrogen atom (H), a and having a portion having a high distribution density C of the atoms (Al), at the interface t _T, the distributed concentration C is considerably lower than that of the support side portion , A suitable example is formed. In this case, the maximum value Cmax of the distribution concentration of the atoms (Al) is preferably at least 10 atomic%, more preferably at least 30 atomic%, and optimally
It is desirable to form a layer so that a distribution state of 50 atomic% or more can be obtained.

In the present invention, the content of atoms (Al) contained in the lower layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably more than 5 atomic% and 95 atomic%. % Or less, more preferably 10 to 90 atomic%,
Most preferably, it is set to 20 to 80 atomic%.

FIGS. 9 to 16 show silicon atoms (Si) contained in the lower layer of the electrophotographic light-receiving member of the present invention;
A typical example of a distribution state of a hydrogen atom (H), a halogen atom (X), an atom (CNOc) contained as necessary, and an atom (Mc) in a layer thickness direction is shown.

9 to 16, the horizontal axis is the silicon atom (S
i), hydrogen atom (H), halogen atom (X), atom (CNO
c), atom (Mc) (hereinafter collectively referred to as “atom (SH
X) ". However, the distribution states of silicon atoms (Si), hydrogen atoms (H), atoms (X), atoms (CNOc), and atoms (Mc) in the layer thickness direction may be the same or different.) the C, the vertical axis represents the thickness of the lower layer, t _B is the position of the end face of the lower layer on the support side, t _T represents the position of the end face of the lower layer of the upper layer side. That is, the lower layer contained the atoms (SHX) is a layer formed toward the t _T side from t _B side.

FIG. 9 shows a first typical example of a distribution state of atoms (SHX) contained in the lower layer in the layer thickness direction.

In the example shown in FIG. 9, the distribution concentration C of the contained atoms (SHX) increases linearly from the concentration C ₉₁ from the position t _B to the position t ₉₁ , and increases from the position t ₉₁ to the position t Until _T, a distribution state is formed such that the concentration C ₉₂ takes a constant value.

In the example shown in FIG. 10, the distribution concentration C of the atoms contained (SHX) is to the position t _T to the position t _B is increased from the concentration C ₁₀₁ a linear function, the concentration C ₁₀₂ at position t _T A distribution state as follows is formed.

In the example shown in Figure 11, the distribution concentration C of the atoms contained (SHX), the concentration C at position t _T increases gradually continuously from the position t _B to the position t concentrations up to _T C ₁₁₁ A distribution state such as ₁₁₂ is formed.

In the example shown in FIG. 12, the distribution concentration C is next concentration C ₁₂₂ at position t ₁₂₁ to increase from the concentration C ₁₂₁ linear function manner up to the position t ₁₂₁ to the position t _B of the atoms contained (SHX) , to the position t _T to the position t ₂₀₁ forms a kind of distribution takes a constant value the concentration C ₁₂₃ becomes.

In the example shown in FIG. 13, the distribution concentration C is the concentration C ₁₃₂ at position t ₁₃₁ gradually increases continuously from the concentration C ₁₃₁ up to the position t ₁₃₁ to the position t _B of the atoms contained (SHX) next, to the position t _T to the position t ₁₃₁ forms a kind of distribution takes a constant value consisting concentration C _133.

In the example shown in FIG. 14, the distribution concentration C of the contained atoms (SHX) gradually increases continuously from the concentration C ₁₄₁ from the position t _B to the position t _T , and then increases at the position t _T. A distribution state of ₁₄₂ is formed.

In the example shown in FIG. 15, the distribution concentration C of the atoms contained (SHX) in the case of substantially zero (below the detection limit amount is substantially zero, where up to a position t ₁₅₁ to the position t _B Is,
The same applies to the meaning of “substantially zero” hereinafter), gradually increasing to the density C ₁₅₁ at the position t ₁₅₁ , and taking a constant value of the density C ₁₅₂ from the position t ₁₅₁ to the position t _T. Distribution state.

In the example shown in FIG. 16, the distribution concentration C of the atoms contained (SHX) includes a concentration C ₁₆₁ at position t _T is gradually increased from substantially zero up to the position t _T to the position t _B A distribution state is formed as follows.

As described above with reference to FIGS. 9 to 16, some typical examples of the distribution of silicon atoms (Si) and hydrogen atoms (H) contained in the lower layer in the layer thickness direction have been described. , at the support side, it comprises aluminum atoms (Al), and silicon atoms (Si), having a distribution density C of the lower part of the hydrogen atom (H), a at the interface t _T, the distributed concentration C is support side In a case where the distribution state of silicon atoms (Si) and hydrogen atoms (H) having portions which are considerably higher than in the case of being provided in the lower layer, a preferable example is formed. In this case, the maximum value Cmax of the distribution concentration of the sum of silicon atoms (Si) and hydrogen atoms (H) is preferably at least 10 at%, more preferably at least 30 at%, and optimally at least 50 at%. It is desirable that the layers are formed so that a distribution state as shown in FIG.

In the present invention, the content of silicon atoms (Si) contained in the lower layer is appropriately determined as desired so as to effectively achieve the object of the present invention. More preferably, it is 10 to 90 atomic%, and most preferably, 20 to 80 atomic%.

In the present invention, the content of hydrogen atoms (H) contained in the lower layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 0.01 to 70 atomic%. More preferably, the content is 0.1 to 50 atomic%, and most preferably 1 to 40 atomic%.

As the halogen atom (X), a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), and an iodine atom (I) are used. In the present invention, the lower layer contains a fluorine atom (F) and / or a chlorine atom (Cl) and / or a bromine atom (Br) and / or an iodine atom (I) as a halogen atom (X). The dangling bonds such as silicon atoms (Si) and aluminum atoms (Al) mainly contained in the lower layer are compensated, and the system quality is stabilized structurally, so that the layer quality can be improved. The content of the halogen atom (X) contained in the lower layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 4 × 10 ⁵ atomic ppm, Preferably 10 to ³ × 10 ⁵ atomic ppm, optimally 1 × 10 ² to 2
It is desirably set to × 10 ⁵ atomic ppm.

The atoms (CNOc) for adjusting the durability contained as required include carbon atoms (C), nitrogen atoms (N),
An oxygen atom (O) is used. In the present invention, carbon atoms (C) are used as atoms (CNOc) for adjusting durability in the lower layer.
And / or containing a nitrogen atom (N) and / or an oxygen atom (O) to improve the charge injection property mainly between the aluminum-based support and the upper layer, and / or The effect of improving the charge transportability and / or the effect of improving the adhesion between the aluminum-based support and the upper layer can be obtained. Further, the effect of controlling the forbidden band width can be obtained in a layer region where the content of aluminum atoms (Al) is small in the lower layer. The atoms that adjust the durability contained in the lower layer (CN
The content of Oc) is preferably 1 × 10 ^{1 to} 5 × 10 ⁵ atoms.
ppm, more preferably 5 × 10 ¹ to 4 × 10 ⁵ atomic ppm, and most preferably 1 × 10 ^{2 to} 3 × 10 ³ atomic ppm.

The atoms (Mc) for adjusting the image quality contained as necessary include those in the periodic table II except aluminum atoms.
An atom belonging to Group I (hereinafter abbreviated as “Group III”), an atom belonging to Group V of the periodic table excluding nitrogen atom (N) (hereinafter abbreviated as “Group V atom”), an oxygen atom (O ) Except for those belonging to Group VI of the periodic table (hereinafter abbreviated as "Group VI atoms"). As the Group III atom, specifically,
There are B (boron), Ga (gallium), In (indium), (thallium) and the like, and B and Ga are particularly preferable. Specific examples of Group V atoms include P (phosphorus), As (arsenic), Sb (antimony), and Bi (bismuth), with P and As being particularly preferred. Specific examples of Group VI atoms include S (sulfur), Se
(Selenium), Te (tellurium), Po (polonium), etc.
Particularly, S and Se are preferable. In the present invention, a group III atom or a group V atom is used as an atom (Mc) for adjusting image quality in the lower layer.
By containing a group atom or a group VI atom, the effect of improving the charge injection property mainly between the aluminum-based support and the upper layer and / or the effect of improving the charge traveling property in the lower layer can be obtained. Obtainable. Further, in the layer region where the content of aluminum atoms (Al) is small in the lower layer, the effect of controlling the conductivity type and / or conductivity can be obtained. The content of atoms (Mc) for adjusting the image quality contained in the lower layer is preferably 1 ×
10 ^{−3 to} 5 × 10 ⁴ atomic ppm, more preferably 1 × 10 ⁻² to 1 ×
It is desirable that the concentration be 10 ⁴ atomic ppm, optimally 1 × 10 ^{-1 to} 5 × 10 ³ atomic ppm.

In the present invention, the lower layer made of AlSiH is created, for example, by the same vacuum deposition film forming method as the upper layer described later, by appropriately setting the numerical conditions of the film forming parameters so as to obtain desired characteristics. You. Specifically, for example, glow discharge method (AC discharge CVD such as low frequency CVD, high frequency CVD or microwave CVD, or DC discharge CVD, etc.), ECR
-Activated species (A) generated by decomposing the raw material gas of CVD, sputtering, vacuum deposition, ion plating, photo-CVD, and chemical interaction with the activated species (A) A method of separately introducing an active species (B) generated from a chemical substance for film formation into a film formation space for forming a deposited film, and chemically reacting them to form a material. (Hereinafter abbreviated as “HRCVD method”). A raw material gas of a material and a halogen-based oxidizing gas having a property of oxidizing the raw material gas are separately introduced into a film formation section for forming a deposited film, and the material is chemically reacted to thereby form the material. Forming method (hereinafter “FOCV
Abbreviated as "D method"). These thin film deposition methods depend on manufacturing conditions,
It is appropriately selected and adopted depending on factors such as the load degree under capital investment, the manufacturing scale, and the characteristics desired for the electrophotographic light-receiving member to be produced. Glow discharge method, sputtering method, ion plating method, etc., because it is relatively easy to control the conditions for the production and it is possible to easily introduce hydrogen atoms together with aluminum atoms and silicon atoms. HRCVD and FOCVD are preferred. These methods may be used together in the same apparatus system.
For example, in order to form a lower layer composed of AlSiH by a glow discharge method, a raw material gas for supplying Al that can basically supply aluminum atoms (Al) and a silicon gas (Si) can be supplied. Si supply gas and hydrogen atom (H)
Supply gas capable of supplying hydrogen, X supply gas capable of supplying halogen atoms (X), CNOc supply gas capable of supplying atoms (CNOc) for adjusting durability as required, and A gas for supplying atoms capable of supplying atoms (Mc) for adjusting the image quality is introduced under a desired gas pressure state into a deposition chamber in which the inside can be reduced in pressure, and a glow discharge is generated in the deposition chamber, and a predetermined A layer made of AlSiH may be formed on the surface of a predetermined support provided at the position.

In order to form the lower layer composed of AlSiH by HRCVD method, it can basically supply aluminum atoms (Al)
Source gas for supplying Al, gas for supplying Si that can supply silicon atoms (Si), and X that can supply halogen atoms (X)
Supply gas and, if necessary, atoms to adjust durability (CN
The gas for supplying CNOc that can supply Oc) and the gas for supplying Mc that can supply atoms (Mc) for adjusting the image quality as needed can be separately or jointly reduced in pressure as needed. The active species (A) is generated by introducing glow discharge into the activation space or heating it in the activation space by introducing the activated species into the activation space provided at the previous stage in the deposition chamber. A source gas for supplying H capable of supplying atoms (H) is similarly introduced into another activation space to generate an active species (B), and the active species (A) and the active species (B) are separately separated. A layer made of AlSiH may be formed on a predetermined support surface which has been introduced into the deposition chamber and previously set at a predetermined position.

In order to form the lower layer composed of AlSiH by FOCVD method, basically, aluminum atoms (Al) can be supplied
Source gas for supplying Al, gas for supplying Si that can supply silicon atoms (Si), gas for supplying H that can supply hydrogen atoms (H), and gas for supplying X that can supply halogen atoms (X) A gas, a CNOc supply gas that can supply atoms for adjusting durability (CNOc) as necessary, and a Mc supply gas that can supply atoms (Mc) for adjusting image quality as necessary are required. Depending on the desired gas pressure, the gas is introduced separately or together into a deposition chamber whose interior can be reduced in pressure, and further halogen (X)
A gas is introduced into the deposition chamber at a desired gas pressure separately from the source gas, and these gases are chemically reacted in the deposition chamber to form AlSiH on a predetermined support surface previously set at a predetermined position. May be formed.

When formed by a sputtering method, for example, Ar,
Use a target composed of Al, a target composed of Si, or a target composed of Al and Si in an atmosphere of an inert gas such as He or a mixed gas based on these gases. Then, a source gas for supplying H that can supply hydrogen atoms (H), a gas for supplying X that can supply halogen atoms (X), and atoms (CNOc) that adjust durability as necessary are supplied. A gas for supplying CNOc that can be supplied and a gas for supplying Mc that can supply atoms (Mc) for adjusting the image quality as necessary are introduced into a deposition chamber for sputtering, and further, if necessary, aluminum atoms (Al) are introduced. A source gas for supplying Al that can be supplied and / or a gas for supplying Si that can supply silicon atoms (Si) are introduced into a deposition chamber for sputtering to form a plasma atmosphere of a desired gas. .

In the case of the ion plating method, for example, aluminum and polycrystalline silicon or single crystal silicon are respectively housed in an evaporation board as an evaporation source, and the evaporation source is subjected to a resistance heating method or an electron beam method (EB method) or the like. It can be performed in the same manner as in the case of the sputtering method, except that it is heated and evaporated, and the flying evaporant is passed through a desired gas plasma atmosphere.

In the present invention, when the lower layer is formed, aluminum atoms (Al), silicon atoms (Si), hydrogen atoms (H), halogen atoms (X) contained in the lower layer, and a Atom (CNOc) for adjusting the quality and Atom (Mc) for adjusting the image quality (hereinafter collectively referred to as “atom (AS
H)) to form a layer having a desired distribution in the thickness direction by changing the distribution concentration C in the thickness direction (glow discharge method, HRCVD method, FOCVD method).
In the case of the method, the atom whose distribution concentration should be changed (ASH)
The supply source gas is formed by appropriately changing the gas flow rate in accordance with a desired rate-of-change curve and introducing the gas into the deposition chamber.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system is appropriately changed by a method usually used such as a manual or external drive motor.

When formed by the sputtering method, the atom (AS
To change the distribution concentration C of H) in the layer thickness direction to form a layer having a desired distribution state (depth profile) in the layer thickness direction, first, as in the case of the glow discharge method,
The raw material for supplying atoms (ASH) is used in a gas state, and the gas flow rate is appropriately changed according to a desired change rate curve,
This is done by introducing into the deposition chamber.

Second, a sputtering target such as Al
If you use a target mixed with Si and
This is achieved by changing the mixing ratio of Al and Si in the thickness direction of the target in advance.

AlCl ₃ , AlBr ₃ , AlI ₃ , Al (CH ₃ ) ₂ Cl, Al (CH ₃ ) ₃ , Al
(OCH ₃ ) ₃ , Al (C ₂ H ₅ ) ₃ , Al (OC ₂ H ₅ ) ₃ , Al (iC ₄ H ₉ ) ₃ , Al (iC
₃ H ₇ ) ₃ , Al (C ₃ H ₇ ) ₃ , Al (OC ₄ H ₉ ) _{3 and the} like are effectively used. Further, the raw material gas for supplying Al may be used after being diluted with a gas such as H ₂ , He, Ar, or Ne as needed.

Examples of the substance that can be a raw material gas for supplying Si used in the present invention include silicon hydride in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ or a gasizable silicon hydride ( Silanes), and SiH ₄ , Si ₂ H _{6 in} terms of ease of handling at the time of layer preparation and good Si supply efficiency.
Are preferred. Further, these raw material gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

Many halogen compounds are effective as the halogen supply gas used in the present invention. For example, halogen compounds in gaseous state or gasizable halogen compounds such as halogen gas, halides, interhalogen compounds, and halogen-substituted silane derivatives. Are preferred.

Further, in the present invention, a silicon hydride compound containing a halogen atom, which is a gas state or can be gasified, which has a silicon atom and a halogen atom as constituent elements, can be mentioned as an effective one.

The halogen compounds that can be preferably used in the present invention, specifically, fluorine, chlorine, bromine, halogen gas _{iodine, BrF, ClF, ClF 3,} BrF 5, BrF 3, IF 3, IF 7, ICl, Interhalogen compounds such as IBr can be mentioned.

As a silicon compound containing a halogen atom, a silane derivative substituted with a so-called halogen atom, specifically, for example, silicon halides such as SiH ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ can be preferably mentioned. .

When forming a characteristic light receiving member for electrophotography of the present invention by the glow discharge method or the HRCVD method using such a silicon compound containing a halogen atom, a silicon hydride gas is used as a gas for supplying Si. Without this, a lower layer made of AlSiH containing a halogen atom can be formed on a desired support.

When the lower layer containing a halogen atom is formed according to the glow discharge method or the HRCVD method, basically, for example, by using silicon halide as a gas for supplying Si, the lower layer is formed on a desired support. However, in order to further facilitate the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is mixed with these gases to form a layer. May be.

In addition, each gas may be used alone or in combination of a plurality of gases at a predetermined mixing ratio.

In the present invention, the above-described halogen compounds or halogen-containing silicon compounds are effectively used as the halogen atom supply gas, but other halogenated compounds such as HF, HCl, HBr, and Hl may be used. Hydrogen, SiH ₃ F, SiH
_{2 F 2, SiHF 3, SiH} 2 I 2, SiS 2 Cl 2, SiHCl 3, SiH 2 Br 2, SiHBr halogenated silicon hydride, lower layer or material is also enabled that can be gasified in like gaseous state, such as ₃ It can be mentioned as a raw material for formation. Among these substances, a halide containing a hydrogen atom introduces a halogen atom into the layer at the time of forming the lower layer, and simultaneously introduces a hydrogen atom which is extremely effective in controlling electric or photoelectric characteristics. In the present invention, it is used as a suitable halogen supply gas.

In order to introduce hydrogen atoms structurally into the lower layer, in addition to the above, supply H ₂ or silicon hydride such as SiH ₄ , SiH ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ and Si Can also be performed by causing silicon or a silicon compound to coexist in the deposition chamber to generate a discharge.

In order to control the amount of hydrogen atoms (H) and / or halogen atoms (X) that can be contained in the lower layer, for example, in order to contain the support temperature and / or hydrogen atoms (H) or halogen atoms (X) What is necessary is just to control the amount of the raw material used for the introduction into the deposition system, the discharge power, and the like.

In order to structurally introduce durability-adjusting atoms (CNOc), for example, carbon atoms (C), nitrogen atoms (N), or oxygen atoms (O) into the lower layer, it is necessary to use carbon atoms during layer formation. (C) A source material for introduction, a source material for introduction of nitrogen atoms (N), or a source material for introduction of oxygen atoms (O) in a gaseous state in a deposition chamber, and another source material for forming a lower layer. It should be introduced together with. Carbon atom (C)
The raw material for introduction, the raw material for introduction of nitrogen atoms (N) or the raw material for introduction of oxygen atoms (O) can be gaseous at ordinary temperature and normal pressure, or easily at least under conditions of layer formation. It is desirable to employ a material that can be gasified.

Starting materials that can be effectively used as a source gas for introducing carbon atoms (C) include C and H as constituent atoms, for example, a saturated hydrocarbon having 1 to 4 carbon atoms, and a C 2 to 2 carbon atom.
4 ethylene-based hydrocarbons, and acetylene-based hydrocarbons having 2 to 3 carbon atoms.

Specifically, as the saturated hydrocarbon, methane (C
H _4), ethane (C ₂ H _6), propane (C ₃ H _8), n- butane (nC ₄ H _10), pentane (C ₅ H _12), as the ethylenic hydrocarbons, ethylene (C ₂ H _4), propylene (C ₃ H _6), butene -1 (C ₄ H _8), butene--2 (C ₄ H _8), isobutylene (C ₄ H _8), pentene (C ₅ H _10), acetylenic hydrocarbons As hydrogen, acetylene (C ₂ H ₂ ), methyl acetylene (C ₃
H ₄ ) and butyne (C ₄ H ₆ ).

As a source gas containing Si and C as constituent atoms, Si (C
Examples thereof include alkyl silicides such as H ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ .

In addition, CF ₄ , CCl ₄ , CH ₃ CF can be introduced in addition to the introduction of carbon atoms (C).
_And halogenated carbon gas such as ₃ .

A source material that is effectively used as a source gas for introducing a nitrogen atom (N) has N as a constituent atom.
Alternatively, for example, nitrogen (N ₂ ) having N and H as constituent atoms,
Gaseous or gasifiable nitrogen such as ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen such as nitride and azide Compounds can be mentioned. In addition, nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F
₄ N ₂ ) and the like.

Starting materials that can be effectively used as source gas for introducing oxygen atoms (O) include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), and nitrogen dioxide (NO ₂ ). ,
Nitrogen dioxide (N ₂ O), nitrogen trioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), N nitrogen oxide (NO
₂ ), silicon atoms (Si), N atoms (O), hydrogen atoms (H), and constituent atoms such as didioxane (H ₃ SiOS
lower siloxanes such as iH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ).

In the lower layer, there are atoms (Mc) that adjust the image quality, for example,
In order to structurally introduce a group III atom, a group V atom, or a group VI atom, a source material for introducing a group III atom, a source material for introducing a group V atom, or a VI A raw material for introducing group atoms may be introduced in a gaseous state into the deposition chamber together with another raw material for forming the lower layer. The source material for introducing a group III atom, the source material for introducing a group V atom, or the source material for introducing a group VI atom may be gaseous at normal temperature and normal pressure or at least under conditions for forming a layer. It is desirable to employ a material which can be easily gasified. As such a raw material for introducing a Group III atom, specifically, 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
Examples include boron hydride such as _{14 and the} like, and boron halide such as BF ₃ , BCl ₃ and BBr ₃ . In addition, Gal ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl ₃
And the like.

As a raw material for introducing a group V atom, in the present invention, PH ₃ , P ₂
H _4, etc. of hydrogen phosphorus _{halides, PH 4 I, PF 3,} PF 5, PCl 3, PCl 5, PBr 3, PBr 5, P
And phosphorus halides such as I ₃ . In addition, ASH ₃ , AsF
_{3, AsCl 3, AsBr 3,} AsF 5, SbH 3, SbF 3, SbCl 3, SbCl 5, BiH 3, BiCl
₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing Group V atoms.

As a raw material for introducing a Group VI atom, hydrogen sulfide (H _{2
S), SF 4, SF 6} , SO 2, SO 2 F 2, COS, CS 2, CH 3 SHC 2 H 5 SH, C 4 S 4 H,
Substances in a gaseous state or capable of being gasified, such as (CH ₃ ) ₂ S (C ₂ H ₅ ) ₂ S, are mentioned. In addition, SeH ₂ , SeF ₆ , (CH ₃ ) ₂ Se, (C ₂ H ₅ ) ₂
Substances in a gaseous state or gasifiable substances such as Se, TeH ₂ , TeF ₆ , (CH ₃ ) ₂ Te, and (C ₂ H ₅ ) ₂ Te are exemplified.

Further, these raw materials for introducing atoms (Mc) for controlling the image quality may be used by diluting them with a gas such as H ₂ , He, Ar, or Ne as necessary.

The thickness of the lower layer in the present invention is from 0.003 to from the viewpoint of obtaining desired electrophotographic properties, and economic effects.
5 μm, preferably 0.01-1 μm, optimally 0.05-0.5
μm is desirable.

In the present invention, the end face of the lower layer with the aluminum-based support is formed by the aluminum atom (Al) of the lower layer.
Is a region in which the content of aluminum atoms is 95% or less of the content of aluminum atoms (Al) in the aluminum-based support. This means that the aluminum atom (Al) content is 95% of the aluminum atom (Al) content in the aluminum-based support.
This is because, in the region of the composition exceeding, the function has almost only the function of the support. Further, the end face of the lower layer with the upper layer is a region where the content of aluminum atoms (Al) in the lower layer exceeds 5%. This is because, in a region having a composition in which the content of aluminum atoms (Al) is 5% or less, almost all of the functions have only the function of the upper layer.

In order to form a lower layer made of AlSiH having characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the gas pressure in the deposition chamber and the temperature of the support as desired.

Gas pressure in the deposition chamber can be appropriately selected within an optimum range in accordance with the layer design, usually 1 × 10 ^-5 to 10 Torr, preferably ^{1 × 10 -4 ~3Torr, 1 ×} 10 -4 ~1Torr optimally It is preferred that

The support temperature (Ts) is appropriately selected in an optimum range according to the layer design, but is usually 50 to 600 ° C, preferably 100 to 600 ° C.
Preferably, the temperature is 400 ° C.

In the present invention, when the lower layer made of AlSiH is formed by a glow discharge method, an optimal range is appropriately selected according to the layer design for the discharge power to be supplied into the deposition chamber, but usually 5 × 10 ^{−5 to} 10 W / cm ³ , preferably 5 × 10 ^{-4 to} 5 W /
cm ³ , optimally 1 × 10 ⁻³ to 2 × 10 ⁻¹ W / cm ³ .

In the present invention, the gas pressure in the deposition chamber for forming the lower layer, the temperature of the support, the above-mentioned range as a desirable numerical range of the discharge power to be supplied into the deposition chamber, may be mentioned,
These layer formation factors are not usually independently determined separately, but are optimally determined based on mutual and organic relevance in order to form a lower layer having desired characteristics. It is desirable to decide.

Upper Layer The upper layer in the present invention is made of Non-Si (H, X) and has desired photoconductive properties.

In the present invention, at least the carbon layer (C) and / or the nitrogen atom (N) and / or the oxygen atom (O) are contained in the layer region in contact with at least the lower layer of the upper layer, and the conductivity is controlled as necessary. May be contained, but neither a germanium atom (Ge) nor a tin atom (Sn) is substantially contained. However, in the other layer regions of the upper layer, there are atoms (M) controlling conductivity, carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), germanium atoms (Ge), tin atoms ( At least one of Sn) may be contained. In particular, the layer region near the free surface of the upper layer preferably contains at least one of carbon atoms (C), nitrogen atoms (N), and oxygen atoms (O).

Controlling carbon atoms (C) and / or nitrogen atoms (N) and / or oxygen atoms (O) contained in at least the layer region in contact with the lower layer of the upper layer and / or the conductivity contained as required Atoms (M) may be uniformly distributed in the layer region, or may be uniformly distributed in the layer region, but are unevenly distributed in the layer thickness direction. There may be a part contained in a state. However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary to be uniformly contained in a uniform distribution from the viewpoint of achieving uniform characteristics in the in-plane direction. .

At least a layer (M), a carbon atom (C), a nitrogen atom (N), an oxygen atom (O), a germanium atom (G
e), when containing at least one of tin atoms (Sn), the above-mentioned conductivity controlling atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), germanium atoms ( Ge) and tin atoms (Sn) may be uniformly distributed in the layer region, or may be uniformly distributed in the layer region, but may be unevenly distributed in the layer thickness direction. Some parts may be contained in a distributed state. However, even in any case, in the in-plane direction parallel to the surface of the support, it is necessary to contain evenly and without unevenness from the viewpoint of achieving uniform characteristics in the in-plane direction. is there.

Further, a layer region (hereinafter abbreviated as “layer region (M)”) containing atoms (M) for controlling conductivity (hereinafter abbreviated as “atom (M)”), carbon atoms (C) and / or Or a layer region in contact with at least a lower layer of an upper layer containing a nitrogen atom (N) and / or an oxygen atom (O) (hereinafter abbreviated as “atom (CNO)”) (hereinafter “layer region (CNO _B )”)
) May be substantially the same layer region, or may share at least a part of the surface side of the layer region (CNO _B ).

Further, a layer region containing germanium atoms (Ge) and / or tin atoms (Sn) (hereinafter abbreviated as “atom (GS)”) (hereinafter abbreviated as “layer region (GS)”) is a layer region ( Part of the surface side of CNO _B ) may be shared.

Further, a layer region containing atoms (CNO) other than the layer region (CNO _B ) (hereinafter abbreviated as “layer region (CNO _T )”, and the layer region (CNO _B ) and the layer region (CNO _T ) are collectively referred to. "Layer area (CN
O) "), the layer area (M), and the layer area (GS)
May be substantially the same layer region, may share at least a part of each layer region, or may not substantially share each layer region.

FIGS. 17 to 36 show typical examples of the distribution of atoms (M) contained in the layer region (M) in the layer thickness direction in the upper layer of the electrophotographic light-receiving member of the present invention. A typical example of the distribution of atoms (CNO) in the region (CNO) in the layer thickness direction is shown, and a typical example of the distribution of atoms (GS) in the layer region (GS) in the layer thickness direction is shown. It is a thing. (Hereinafter, the layer region (M), the layer region (CNO), and the layer region (GS) are referred to as “layer region (Y)”, and the atom (M) and the atom (CN
O) and the atom (GS) are represented as “atom (Y)”. Accordingly, FIGS. 17 to 36 show typical examples of the distribution state of the atoms (Y) contained in the layer region (Y) in the layer thickness direction. (M), layer area (CN
O), when the layer regions (GS) are substantially the same layer region, the layer region (Y) is singularly included in the upper layer, and when the layer regions (GS) are not substantially the same layer region, the layer region (Y) is not included. Y) are included in the upper layer plurally).

In Figure 17 to Figure 36, the distribution concentration C of the horizontal axis atom (Y), the end face of the vertical axis represents the layer thickness of the layer region (Y), t _B is the lower layer side layer region (Y) the position, t _T represents the position of the end face of the free surface side layer region (Y). That is, the layer region (Y) contained the atoms (Y) is a layer formed toward the t _T side from t _B side.

FIG. 17 shows the atoms (Y) contained in the layer region (Y).
A first typical example of the distribution state in the layer thickness direction is shown.

In the example shown in FIG. 17, the distribution concentration C of the contained atoms (Y) gradually and continuously increases from the concentration C ₁₇₁ to the position t _T from the position t _B , and the concentration C at the position t _T. A distribution state of ₁₇₂ is formed.

In the example shown in Figure 18, the distribution concentration C of the atoms contained (Y), the concentration C ₁₈₂ at position t ₁₈₁ to increase from the concentration C ₁₈₁ temporary function to up to the position t ₁₈₁ to the position t _B From the position t ₁₈₁ to the position t _T, a distribution state is formed such that the density C ₁₈₃ takes a constant value.

In the example shown in FIG. 19, the distribution concentration C of the atoms contained (Y) becomes a constant value consisting concentration C ₁₉₁ up to the position t ₁₉₁ to the position t _B, reaches the position t ₁₉₂ to the position t ₁₉₁ The density gradually increases continuously from the density C ₁₉₁ until _reaching the density C ₁₉₂ at the position t ₁₉₂ , and forms a distribution state in which the density C ₁₉₃ takes a constant value from the position t ₁₉₂ to the position t _T.

In the example shown in FIG. 20, the distribution concentration C of the contained atoms (Y) has a constant value of the concentration C ₂₀₁ from the position t _B to the position t _201, and reaches the position t ₂₀₂ from the position t _201. until it becomes constant value consisting concentration C _202, to the position t _T to the position t ₂₀₂ forms a distribution state such as taking a constant value that is the concentration C _203.

In the example shown in FIG. 21, the distribution concentration C of the atoms contained (Y) is, to the position t _T to the position t _B forms a distribution such as a constant value consisting concentration C _211.

In the example shown in FIG. 22, the distribution concentration C of the atoms contained (Y) is up to the position t ₂₂₁ to the position t _B takes a constant value the concentration C ₂₂₁ becomes, leading to the position t _T to the position t ₂₂₁ Concentration C _{222 up to}
From the concentration C _{223 at the} position t _T.
A distribution state as follows is formed.

In the example shown in FIG. 23, the distribution concentration C of the atoms contained (Y) gradually decreases continuously from the concentration C ₂₃₁ up to the position t _T to the position t _B, the concentration at position t _T forming a kind of distribution becomes C _232.

In the example shown in FIG. 24, until the distribution concentration C of the atoms contained (Y) leads to a position t _T to the position t ₂₄₁ until the position t ₂₄₁ to the position t _B takes a constant value consisting concentration C ₂₄₁ gradually decreases continuously from the concentration C _242, the distribution concentration C at position t _T
Is substantially zero (where substantially zero is less than the detection limit amount, and the meaning of “substantially zero” hereinafter is the same).

In the example shown in FIG. 25, the distribution concentration C of the atoms contained (Y) gradually decreases continuously from the concentration C ₂₅₁ up to the position t _T to the position t _B, the distribution at the position t _T The concentration C forms a distribution state that becomes substantially zero.

In the example shown in FIG. 26, the distribution concentration C of the atoms contained (Y) is up to the position t ₂₆₁ to the position t _B takes a constant value consisting concentration C _261, reaches the position t _T to the position t ₂₆₁ Up to concentration C ₂₆₁
And linearly decreases to a form a kind of distribution that the concentration C ₂₆₂ at position t _T.

In the example shown in FIG. 27, the distribution concentration C of the contained atom (Y) decreases linearly from the concentration C ₂₇₁ from the position t _B to the position t _T, and the distribution concentration C at the position t _T C forms a distribution state that becomes substantially zero.

In the example shown in FIG. 28, the distribution concentration C of the atoms contained (Y) is up to the position t ₂₈₁ to the position t _B takes a constant value consisting concentration C _281, reaches the position t _T to the position t ₂₈₁ Up to C ₂₈₁
And linearly decreases to a form a kind of distribution that the concentration C ₂₈₂ at position t _T.

In the example shown in FIG. 29, the distribution concentration C of the contained atoms (Y) gradually and continuously decreases from the concentration C ₂₉₁ from the position t _B to the position t _T , and at the position t _T to form a such a distribution state becomes the C _292.

In the example shown in FIG. 30, the distribution concentration C of the atoms contained (Y) takes a constant value to the position t ₃₀₁ is made concentration C ₃₀₁ from the position t _B, to the position t _T to the position t ₃₀₁ is reduced from the concentration C ₃₀₂ linear function to form a kind of distribution that the concentration C ₃₀₃ at position t _T.

In the example shown in FIG. 31, the distribution concentration C of the contained atom (Y) gradually increases continuously from the concentration C ₃₁₁ from the position t _B to the position t ₃₁₁ , and then increases at the position t ₃₁₁ . ₃₁₂ , and a distribution state is formed such that the density C ₃₁₃ takes a constant value from the position t ₃₁₁ to the position t _T.

In the example shown in Figure 32, the distribution concentration C of the atoms contained (Y), the concentration C at position t _T gradually increases continuously from the concentration C ₃₂₁ up to the position t _T to the position t _B A distribution state of ₃₂₂ is formed.

In the example shown in FIG. 33, the distribution concentration C of the atoms contained (Y) is substantially zero (below the detection limit amount substantially zero here up to the position t ₃₃₁ to the position t _B Is the case,
The same applies to the meaning of “substantially zero” hereinafter), gradually increasing to a density C ₃₃₁ at a position t ₃₃₁ , and taking a constant value of a density C ₃₃₂ from the position t ₃₃₁ to the position t _T. Distribution state.

In the example shown in FIG. 34, the distribution concentration C of the atoms contained (Y) includes a concentration C ₃₄₁ at position t _T is gradually increased from substantially zero up to the position t _T to the position t _B A distribution state is formed as follows.

In the example shown in FIG. 35, the distribution concentration C of the contained atoms (Y) increases linearly from the concentration C ₃₅₁ from the position t _B to the position t ₃₅₁ and then increases from the position t ₃₅₁ to the position t. Up to _T, a distribution state in which the concentration C ₃₅₂ takes a constant value is formed.

In the example shown in FIG. 36, the distribution concentration C of the atoms contained (Y) is, to the position t _T to the position t _B is increased from the concentration C ₃₆₁ a linear function, the concentration C ₃₆₂ at position t _T A distribution state as follows is formed.

As the atom (M) for controlling the conductivity, a so-called impurity in the semiconductor field can be mentioned. In the present invention, the periodic table III which gives p-type conductivity is used.
Group V atoms (hereinafter abbreviated as "Group V atoms") except for those belonging to Group V (hereinafter abbreviated as "Group III atoms") or those belonging to Group V of the periodic table excluding nitrogen atoms (N) that impart n-type conduction properties. ) And an atom belonging to Group VI of the periodic table except for an oxygen atom (O) (hereinafter abbreviated as “Group VI atom”). No.
Specific examples of Group III atoms include B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium), with B, Al, and Ga being particularly preferred. Specific examples of Group V atoms include P (phosphorus), As (arsenic), Sb (antimony), and Bi (bismuth), with P and As being particularly preferred. Specific examples of Group VI atoms include S (sulfur), Se (selenium), Te (tellurium), and Po (polonium), with S and Se being particularly preferred. In the present invention, the layer region (M) has the third group as the atom (M) for controlling conductivity.
The effect of mainly controlling the conductivity type and / or the conductivity by containing a group atom, a group V atom or a group VI atom and / or a layer region (M) and a layer other than the layer region (M) of the upper layer The effect of improving the charge injecting property with the region can be obtained. The content of the atom (M) for controlling conductivity contained in the layer region (M) is preferably 1 × 10 ^{−3 to} 5 × 10 ⁴ atomic ppm, more preferably 1 × 10 ^−2.
~ 1 × 10 ⁴ atomic ppm, optimally 1 × 10 ^{-1 to} 5 × 10 ³ atomic ppm
It is desirable to be. In particular, when the content of carbon atoms (C) and / or nitrogen atoms (N) and / or oxygen atoms (O) described later in the layer region (M) is 1 × 10 ³ atomic ppm or less, the layer region (M) The content of the atom (M) for controlling the conductivity contained in the metal is preferably 1 × 10 ⁻³ to 1
× is desirable are 10 ³ atomic ppm, and if the content of carbon atoms (C) and / or nitrogen atom (N) and / or oxygen atoms (O) exceeds 1 × 10 ³ atomic ppm, conductivity The content of the atom (M) for controlling
Desirably, the concentration is from 10 ^{-1 to} 5 x 10 ⁴ atomic ppm.

In the present invention, the carbon atom (C) is added to the layer region (CNO).
And / or the inclusion of nitrogen atoms (N) and / or oxygen atoms (O) to increase the dark resistance and / or hardness and / or control the spectral sensitivity and / or the layer area (CNO _B ). The effect of improving adhesion between the lower layer and / or improving adhesion between the layer region (CNO) and the layer region of the upper layer other than the layer region (CNO) can be obtained. The content of carbon atoms (C) and / or nitrogen atoms (N) and / or oxygen atoms (O) contained in the layer region (CNO) is preferably 1 to 9 ×
10 ⁵ atomic ppm, more preferably 1 × 10 ^{1 to} 5 × 10 ⁵ atomic pp
m, and most preferably 1 × 10 ^{2 to} 3 × 10 ⁵ atomic ppm. In particular, it is preferably 1 × 10 ^{3 to} 9 × 10 ⁵ atomic ppm when high dark resistance and / or high hardness are measured, and preferably 1 × 10 ³ atomic ppm when controlling spectral sensitivity. ^It is desirable that the content be ^{2 to} 5 × 10 ⁵ atomic ppm.

In the present invention, by controlling the spectral sensitivity, in particular, by controlling the spectral sensitivity by including germanium atoms (Ge) and / or tin atoms (Sn) in the layer region (GS), a semiconductor laser or the like is used as an image exposure source of an electrophotographic apparatus. When long-wavelength light is used, an effect of improving long-wavelength light sensitivity can be obtained.
The content of germanium atoms (Ge) and / or tin atoms (Sn) contained in the layer region (GS) is preferably 1
9.59.5 × 10 ⁵ atomic ppm, more preferably 1 × 10 ² -8 × 10 ⁵
It is desirable to set the atomic ppm, optimally 5 × 10 ^{2 to} 7 × 10 ⁵ atomic ppm.

Further, the hydrogen atoms (H) and / or the halogen atoms (X) contained in the upper layer in the present invention can compensate for the dangling bonds of silicon atoms and improve the layer quality. The content of hydrogen atoms (H) or the sum of hydrogen atoms (H) and halogen atoms (X) contained in the upper layer is preferably 1 × 10 ^{3 to} 7 × 10 ⁵ atomic ppm. And the content of the halogen atom (X) is preferably 1 to 4 ×
10 ⁵ desirably are atomic ppm. In particular, the content of the carbon atoms (C) and / or nitrogen atoms (N) and / or oxygen atoms (O) in the upper layer is 3 × 10
^When the content is ⁵ atomic ppm or less, the content of the hydrogen atom (H) or the sum of the hydrogen atom (H) and the halogen atom (X) is 1 ×
It is desirable that the concentration be 10 ³ to 4 × 10 ⁵ atomic ppm. further,
When the upper layer is composed of a polycrystalline material, hydrogen atoms (H) contained in the upper layer, or hydrogen atoms (H)
And the content of the sum of halogen atoms (X) is preferably 1 × 10
^The concentration is preferably ^{3 to} 2 × 10 ⁵ atomic ppm, and preferably 1 × 10 ^{4 to} 7 × 10 ⁵ atomic ppm in the case of a non-crystalline material.

In the present invention, the upper layer composed of Non-Si (H, X) can be formed by the same vacuum deposition film forming method as the lower layer described above, and particularly, glow discharge method, sputtering method, ion plating, and the like. Method, HRCVD method and FOCVD method are suitable. These methods may be used together in the same apparatus system.

For example, to form an upper layer composed of Non-Si (H, X) by a glow discharge method, a gas for supplying Si that can supply silicon atoms (Si) and a gas for supplying hydrogen atoms (H ) And / or an X supply gas that can supply halogen atoms (X) and, if necessary, an M supply gas and / or M that can supply atoms (M) that control conductivity. Or a C supply gas capable of supplying carbon atoms (C) and / or an N supply gas capable of supplying nitrogen atoms (N) and / or an O supply gas and / or germanium capable of supplying oxygen atoms (O) A gas for supplying Ge that can supply atoms (Ge) and / or a gas for supplying Sn that can supply tin atoms (Sn) are introduced at a desired gas pressure state into a deposition chamber in which the pressure can be reduced, and the deposition is performed. Generate glow discharge in the room and On a support surface forming a predetermined advance the lower layer are installed in the location Non-
What is necessary is just to form the layer which consists of Si (H, X).

In order to form the upper layer composed of Non-Si (H, X) by HRCVD method, it is basically necessary to control the Si supply gas that can supply silicon atoms (Si) and the conductivity as needed Supply gas capable of supplying atoms (M) to be converted and / or C supply gas capable of supplying carbon atoms (C) and / or N supply gas and / or oxygen atoms capable of supplying nitrogen atoms (N) A gas for supplying O which can supply (O) and / or a gas for supplying Ge which can supply germanium atoms (Ge) and / or a gas for supplying Sn which can supply tin atoms (Sn) are separated as necessary. At the same time or together with introducing a desired gas pressure state into an activation space provided in a preceding stage in a deposition chamber in which the inside can be decompressed to generate a glow discharge or heat in the activation space. Activated species (A)
Is generated, and a H supply gas capable of supplying a hydrogen atom (H) and / or a halogen supply gas capable of supplying a halogen atom (X) are similarly introduced into another activation space to form an active species (B). And the active species (A) and the active species (B) are separately introduced into the deposition chamber, and the non-active material is placed on the surface of the support on which a predetermined lower layer has been formed and which has been previously set at a predetermined position. What is necessary is just to form the layer which consists of Si (H, X).

In order to form an upper layer composed of Non-Si (H, X) by FOCVD method, basically, a Si supply gas that can supply silicon atoms (Si) and a hydrogen atom (H) are supplied. H-supplying gas to be obtained and, if necessary, atoms for controlling conductivity (M)
Supply of M supply gas capable of supplying nitrogen and / or C supply gas capable of supplying carbon atoms (C) and / or N supply gas capable of supplying nitrogen atoms (N) and / or oxygen atoms (O) A gas for supplying O which can supply O and / or a gas for supplying Ge which can supply germanium atoms (Ge) and / or a gas for supplying Sn which can supply tin atoms (Sn);
If necessary, separately or together, the gas is introduced into the deposition chamber in which the pressure can be reduced, and a halogen (X) gas is introduced into the deposition chamber separately from the supply gas at a desired gas pressure. In this state, these gases are chemically reacted in the deposition chamber, and are placed on the surface of the support on which a predetermined lower layer has been formed, which has been previously set at a predetermined position.
What is necessary is just to form the layer which consists of Non-Si (H, X).

In order to form an upper layer composed of Non-Si (H, X) by a sputtering method or an ion plating method, basically, a known method described in, for example, JP-A-61-59342 or the like is used. What is necessary is just to form.

In the present invention, when the upper layer is formed, atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), and germanium atoms (G) that control conductivity contained in the upper layer are formed.
e), tin atom (Sn) (hereinafter collectively referred to as “atom (M
CNOGS) is changed in the layer thickness direction to obtain a desired distribution state in the layer thickness direction (depth profile).
Glow discharge method, HRCVD method, F
In the case of the OCVD method, the atom whose distribution concentration should be changed (MC
NOGS) This is achieved by introducing a source gas for supply into the deposition chamber by appropriately changing the gas flow rate according to a desired rate-of-change curve.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system is appropriately changed by a method usually used such as a manual or external drive motor.

Examples of the substance that can serve as the Si supply gas used in the present invention include silicon hydride (silanes) in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or the like. ) Are effectively used, and SiH ₄ and Si ₂ H ₆ are more preferable in view of easiness of handling at the time of forming a layer, high Si supply efficiency and the like. Further, these raw material gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

Many halogen compounds are effective as the halogen supply gas used in the present invention. For example, halogen gas, a halogenated compound, an interhalogen compound, a halogenated silane derivative or the like gaseous or gasizable halogen can be used. Compounds are preferred.

Further, in the present invention, a silicon hydride compound containing a halogen atom, which is a gas state or can be gasified, which has a silicon atom and a halogen atom as constituent elements, can be mentioned as an effective one.

The halogen compounds that can be preferably used in the present invention, specifically, fluorine, chlorine, bromine, halogen gas iodine _{element, BrF, ClF, ClF 3,} BrF 5, BrF 3, IF 3, IF 7, ICl, IBr
And the like.

As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, a silicon halide such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiBr ₄ may be mentioned as a preferable one. it can.

When a characteristic electrophotographic light-receiving member of the present invention is formed by a glow discharge method or an HRCVD method using a silicon compound containing such a halogen atom, a silicon hydride gas as a Si supply gas is used. Even if not used, an upper layer made of Non-Si (H, X) containing a halogen atom can be formed on a desired support.

When forming an upper layer containing a halogen atom according to a glow discharge method or an HRCVD method, basically, for example, by using silicon halide as a gas for supplying Si, the upper layer is formed on a desired support. However, in order to further facilitate the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is mixed with these gases to form a layer. May be.

In addition, each gas may be used not only in a single species but also in a mixture of a plurality of species at a predetermined mixture ratio.

In the present invention, the above-described halogen compounds or halogen-containing silicon compounds are effectively used as the halogen atom supply gas, but other halogenated compounds such as HF, HCl, HBr, and HI may be used. Hydrogen, SiH ₃ F, SiH
_{2 F 2, SiHF 3, SiH} 2 I 2, SiH 2 Cl 2, SiHCl 3, SiH 2 Br 2, SiHBr halogenated silicon hydride, or substances effective upper layer can be gasified in like gaseous state, such as ₃ It can be mentioned as a raw material for formation. Among these substances, a halide containing a hydrogen atom is introduced into the layer at the time of forming the upper layer, and at the same time, a hydrogen atom which is extremely effective in controlling electric or photoelectric characteristics is introduced into the layer. In the present invention, it is used as a suitable gas for supplying a haloken.

In order to introduce hydrogen atoms into the upper layer structurally, in addition to the above, supply H ₂ , or silicon hydride such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ and Si Can also be performed by causing silicon or a silicon compound to coexist in the deposition chamber to generate a discharge.

In order to control the amount of hydrogen atoms (H) and / or halogen atoms (X) that can be contained in the upper layer, for example, the support temperature and / or the hydrogen atoms (H) or the halogen atoms (X) are contained. What is necessary is just to control the amount of the raw material used for the introduction into the deposition system, the discharge power, and the like.

In the upper layer, atoms controlling conductivity (M), for example,
In order to introduce a Group III atom, a Group V atom or a Group VI atom structurally, a source material for introducing a Group III atom, a source material for introducing a Group V atom or The source material for introducing the group VI atoms may be introduced in a gas state into the deposition chamber together with other source materials for forming the upper layer. The raw material for introducing a Group III atom, the raw material for introducing a Group V atom, or the raw material for introducing a Group VI atom may be a gaseous material at normal temperature and normal pressure or at least under a layer forming condition. It is desirable to employ a material which can be easily gasified. III
As a raw material for introducing a group atom, specifically, 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
Examples include boron hydride such as _{14 and the} like, and boron halide such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , T
lCl _{3 and the} like can also be mentioned.

As a raw material for introducing a group V atom, in the present invention, PH ₃ , P ₂
H _4, etc. of hydrogen phosphorus _{halides, PH 4 I, PF 3,} PF 5, PCl 3, PCl 5, PBr 3, PBr 5, P
Halogenated phosphorus such as I ₃ and the like. In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , B
iCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing Group V atoms.

As a raw material for introducing a Group VI atom, hydrogen sulfide (H _{2
S), SF 4, SF 6} , SO 2, SO 2 F 2, COS, CS 2, CH 3 SH, C 2 H 5 SH, C 4 H 4 S,
Substances in a gaseous state or capable of being gasified, such as (CH ₃ ) ₂ S and (C ₂ H ₅ ) ₂ S, are mentioned. In addition, SeH ₂ , SeF ₆ , (CH ₃ ) ₂ Se, (C ₂ H ₅ ) ₂
Substances in a gaseous state or gasifiable substances such as Se, TeH ₂ , TeF ₆ , (CH ₃ ) ₂ Te, and (C ₂ H ₅ ) ₂ Te are exemplified.

Further, these raw materials for introducing atoms (M) for controlling conductivity may be diluted with a gas such as H ₂ , He, Ar, or Ne as necessary.

Carbon atoms (C) or nitrogen atoms (N) in the upper layer
Alternatively, in order to introduce oxygen atoms (O) structurally, a raw material for introducing carbon atoms (C), a raw material for introducing nitrogen atoms (N), or an oxygen atom (O) may be used in forming a layer.
The raw material for introduction may be introduced in a gas state into the deposition chamber together with another raw material for forming the upper layer.
The raw material for introducing carbon atoms (C), the raw material for introducing nitrogen atoms (N), or the raw material for introducing oxygen atoms (O) may be gaseous at normal temperature and normal pressure, or at least layered. It is desirable to employ one that can be easily gasified under the forming conditions.

Starting materials that can be effectively used as a source gas for introducing carbon atoms (C) include C and H as constituent atoms, for example, a saturated hydrocarbon having 1 to 4 carbon atoms, and a C 2 to 2 carbon atom.
4 ethylene-based hydrocarbons, and acetylene-based hydrocarbons having 2 to 3 carbon atoms.

Specifically, as the saturated hydrocarbon, methane (C
H _4), ethane (C ₂ H _6), propane (C ₃ H _8), n- butane (nC ₄ H _10), pentane (C ₅ H _12), as the ethylenic hydrocarbons, ethylene (C ₂ H _4), propylene (C ₃ H _6), butene -1 (C ₄ H _8), butene--2 (C ₄ H _8), isobutylene (C ₄ H _8), pentene (C ₅ H _10), acetylenic hydrocarbons As hydrogen, acetylene (C ₂ H ₂ ), methyl acetylene (C
₃ H _4), include butyne (C ₄ H ₆₎ and the like.

The source gas containing Si, C and H as constituent atoms includes Si
Alkyl silicides such as (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ can be mentioned.

In addition, CF ₄ , CCl ₄ , CH ₃ CF can be introduced in addition to the introduction of carbon atoms (C).
_And halogenated carbon gas such as ₃ .

A source material that is effectively used as a source gas for introducing a nitrogen atom (N) has N as a constituent atom.
Alternatively, for example, nitrogen (N ₂ ) having N and H as constituent atoms,
Gaseous or gasifiable nitrogen such as ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ ), nitrogen such as nitride and azide Compounds can be mentioned. In addition, nitrogen trifluoride (F ₃ N) and nitrogen tetrafluoride (F
₄ N ₂ ) and the like.

Starting materials that can be effectively used as a source gas for introducing oxygen atoms (O) include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), and nitrogen dioxide (NO ₂ ). ,
Nitrogen monoxide (N ₂ O), nitrogen trioxide (N ₂ O ₃ ), nitrous oxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₂ ), silicon atom (Si), an oxygen atom (O) and a hydrogen atom (H) as constituent atoms, for example, lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ). Can be.

In order to structurally introduce germanium (Ge) or tin atom (Sn) into the upper layer, a raw material for introducing germanium (Ge) or tin atom (Sn) during layer formation
The raw material for introduction may be introduced in a gas state into the deposition chamber together with another raw material for forming the upper layer.
As a raw material for introducing germanium (Ge) or a raw material for introducing tin atoms (Sn), a gaseous material at normal temperature and normal pressure or a material which can be easily gasified at least under layer forming conditions is adopted. It is desirable to be done.

GeH ₄ , G
e ₂ H ₆ , Ge ₃ H ₈ , Ge ₄ H ₁₀ , Ge ₅ H ₁₂ , Ge ₆ H ₁₄ , Ge ₇ H ₁₆ , Ge ₈ H ₁₈ , Ge ₉ H
Germanium hydride in a gaseous state or capable of being gasified, such as _20, is cited as one that is effectively used.Especially, in terms of ease of handling at the time of forming a layer, good Ge supply efficiency, etc.
GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred.

In addition, GeHF ₃ , GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ , GeH _{3
Cl, GeHBr 3, GeH 2 Br} 2, GeH 3 Br, GeHI 3, GeH 2 I 2, GeH 3 hydrogenated germanium halide of I, _{etc., GeF 4, GeCl 4, GeBr} 4, GeI 4,
Examples include germanium halides such as GeF ₂ , GeCl ₂ , GeBr ₂ , and GeI ₂ .

Substances that can be used as source gas for Sn supply include SnH ₄ , S
n ₂ H ₆ , Sn ₃ H ₈ , Sn ₄ H ₁₀ , Sn ₅ H ₁₂ , Sn ₆ H ₁₄ , Sn ₇ H ₁₆ , Sn ₈ H ₁₈ , Sn ₉ H
₂₀ , etc., which can be used effectively as tin hydrides. In particular, SnH ₄ , Sn ₂ , and the like can be used easily in layer formation work and Sn supply efficiency can be improved.
H ₆ and Sn ₃ H ₈ are preferred.

In addition, SnHF ₃ , SnH ₂ F ₂ , SnH ₃ F, SnHCl ₃ , SnH ₂ Cl ₂ , SnH _{3
Cl, SnHBr 3, SnH 2 Br} 2, SnH 3 Br, SnHI 3, SnH 2 I 2, SnH 3 hydrogenated halogenated tin I _{like, SnF 4, SnCl 4, SnBr} 4, SnI 4, SnF 2, SnC
Substances in the gaseous state or gasifiable substances such as tin halides such as l ₂ , SnBr ₂ and SnI ₂ can also be mentioned as effective starting materials for forming the upper layer.

The layer thickness of the upper layer in the present invention is from 1 to 130 μm from the viewpoint that desired electrophotographic characteristics can be obtained, and economic effects.
m, preferably 3 to 100 μm, and most preferably 5 to 60 μm.

Non-Si (H,
In order to form the upper layer made of X), it is necessary to appropriately set the gas pressure in the deposition chamber and the temperature of the support as desired.

Gas pressure in the deposition chamber can be appropriately selected within an optimum range in accordance with the layer design, usually 1 × 10 ^-5 to 10 Torr, preferably ^{1 × 10 -4 ~3Torr, 1 ×} 10 -4 ~1Torr optimally It is preferred that

A-Si containing a hydrogen atom (H) and / or a halogen atom (X) as an upper layer Non-Si (H, X)
When “A-Si (H, X)” is selected and configured, the optimum range of the support temperature (Ts) is appropriately selected according to the layer design. 400 ° C, preferably 1
It is desirable to set the temperature to 00 to 300 ° C.

Polycrystalline silicon containing a hydrogen atom (H) and / or a halogen atom (X) (hereinafter abbreviated as "Poly-Si (H, X)") with the upper layer being Non-Si (H, X) In the case of selective formation, there are various methods for forming the layer, for example, the following method. One method is to increase the temperature of the support, specifically 400-600.
In this method, the temperature is set to ° C., and the film is deposited on the support by a plasma CVD method.

Another method is to first form an amorphous film on the surface of the support, that is, to form a film on the support at a support temperature of, for example, about 250 ° C. by a plasma CVD method, and then subject the amorphous film to an annealing treatment. This is a method to make it poly. The annealing treatment is performed by adding 400
It is carried out by heating to 600600 ° C. for about 5 to 30 minutes, or by irradiating with laser light for about 5 to 30 minutes.

In the present invention, when the upper layer made of Non-Si (H, X) is formed by the glow discharge method, the discharge power to be supplied into the deposition chamber is appropriately selected in accordance with the layer design. 5 × 10 ^{−5 to} 10 W / cm ³ , preferably 5 × 1
It is desirable that it be 0 ^{-4 to 5} W / cm ³ , optimally 1 × 10 ^-3 to 2 × 10 ^-1 W / cm ³ .

In the present invention, the gas pressure in the deposition chamber for forming the upper layer, the temperature of the support, the above-mentioned range as a desirable numerical range of the discharge power to be supplied into the deposition chamber, but,
These layer formation factors are not usually independently determined separately, but are optimally determined based on mutual and organic relationships to form an upper layer having desired characteristics. It is desirable to decide.

〔Example〕

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 An electrophotographic light-receiving member of the present invention was formed by a high frequency (hereinafter abbreviated as “RF”) glow discharge decomposition method.

FIG. 37 shows an apparatus for manufacturing a light receiving member for electrophotography by an RF glow discharge decomposition method, comprising a source gas supply device 1020 and a deposition device 1000.

The sealed container of the gas cylinder and 1078 1071,1072,1073,1074,1075,1076,1077 in the figure and the raw material gas is sealed in order to form each layer of the present invention, 1071 SiH ₄ gas (Purity 99.99%) cylinder, 1072 H ₂ gas (purity 99.9999
%) Cylinder, 1073 is a CH ₄ gas (purity 99.999%) cylinder, 1
074 is a cylinder of SiF ₄ gas (99.999% purity), and 1075 is a B ₂ H ₆ gas diluted with H ₂ gas (99.999% purity, hereinafter “B ₂ H ₆ /
H ₂ ), 1076 is an NO gas (purity 99.9%) cylinder, 1077 is a He gas (purity 99.999%) cylinder, 1078 is AlCl
₃ (99.99% purity) sealed container.

In the figure, reference numeral 1005 denotes a cylindrical aluminum-based support having an outer diameter of 108 mm and a mirror-finished surface.

First, make sure that the valves 1051 to 1057 of the gas cylinders 1071 to 1077, the inflow valves 1031 to 1037, and the leak valve 1015 of the deposition chamber 1001 are closed.
47. After confirming that the auxiliary valve 1018 was opened, first, the main valve 1016 was opened, and the inside of the deposition chamber 1001 and the gas pipe were evacuated by a vacuum pump (not shown).

Next, when the reading of the vacuum gauge 1017 reached about 1 × 10 ⁻³ Torr, the auxiliary valve 1018 and the outflow valves 1041 to 1047 were closed.

Thereafter, SiH ₄ gas and gas cylinder 10
H ₂ gas from 72, CH ₄ gas from gas cylinder 1073, SiF ₄ gas from gas cylinder 1074, B ₂ H ₆ / H ₂ gas from gas cylinder 1075, NO gas from gas cylinder 1076, He from gas cylinder 1077
Gas is introduced by opening valves 1051 to 1057, and the pressure
Each gas pressure was adjusted to ² kg / cm ² by 1061 to 1067.

Next, the inflow valves 1031 to 1037 were gradually opened, and the above gases were introduced into the mass flow controllers 1021 to 1027. At this time, the He gas from the gas cylinder 1077 is supplied to the mass flow controller 1027 in a sealed container 107 filled with AlCl _3.
Since passing through 8, AlCl ₃ gas diluted with He gas (hereinafter abbreviated as “AlCl ₃ / He”) is introduced.

The temperature of the cylindrical aluminum-based support 1005 installed in the deposition chamber 1001 was heated to 250 ° C. by the heater 1014.

After the preparation for the film formation was completed as described above, the lower layer and the upper layer were formed on the cylindrical aluminum-based support 1005.

To form the lower layer, the outflow valves 1041,1042,1044,1
046, 1047 and the auxiliary valve 1018 are gradually opened to allow SiH ₄ gas, H ₂ gas, SiF ₄ gas, NO gas, and AlCl ₃ / He gas to flow into the deposition chamber 1001 through the gas discharge holes 1009 of the gas introduction pipe 1008. Was. At this time, the flow rate of SiH ₄ gas is 50 SCCM, and the flow rate of H ₂ gas is
10SCCM, SiF ₄ gas flow rate 5SCCM, NO gas flow rate 5SCCM, Al
The mass flow controllers 1021, 1022, 1024, 1026, and 1027 adjusted the flow rates of Cl ₃ / He to be 120 SCCM. The opening of the main valve 1016 was adjusted while watching the vacuum gauge 1017 so that the pressure in the deposition chamber 1001 became 0.4 Torr.
Thereafter, the RF power was introduced into the deposition chamber 1001 through the high-frequency matching box 1012 to set the power of the RF power source (not shown) to 5 mW / cm ^3, to rise to RF glow discharge, the lower layer on a cylindrical aluminum base support on Began to form. During the formation of the lower layer, the flow rate of the SiH ₄ gas was maintained at a constant flow rate of 50 SCCM.
H ₂ gas flow rate to increase at a constant rate to 200SCCM from 10 SCCM, so that a constant flow rate of SiF ₄ gas flow rate and NO gas flow rate are both 5SCCM, AlCl ₃ / He gas flow rate constant for 40SCCM from 120SCCM Adjust the mass flow controllers 1021, 1022, 1024, 1026, 1027 so that they decrease in proportion, and set the layer thickness to 0.
When the lower layer of 05 μm was formed, the RF glow discharge was stopped, and the outflow valves 1041, 1042, 1044, 1046, 1047 and the auxiliary valve 1018 were closed to stop the flow of gas into the deposition chamber 1001. Finished forming.

Next, in order to form the first layer region of the upper layer, the outflow valves 1041, 1042, and 1046 and the auxiliary valve 1018 are gradually opened, and SiH ₄ gas, H ₂ gas, and NO gas are It was allowed to flow into the deposition chamber 1001 through the discharge hole 1009. At this time,
The mass flow controllers 1021, 1022, and 1026 adjusted the SiH ₄ gas flow rate to 100 SCCM, the H ₂ gas flow rate to 100 SCCM, and the NO gas flow rate to 30 SCCM. The pressure in the deposition chamber 1001 is
The opening of the main valve 1016 was adjusted while watching the vacuum gauge 1017 so that the pressure became 0.35 Torr. After that, the power of the RF power supply (not shown) is set to 10 mW / cm ³ and RF power is introduced into the deposition chamber 1001 through the high-frequency matching box 1012 to generate an RF glow discharge, and the first layer of the upper layer is formed on the lower layer. The formation of the layer region is started, and the RF glow discharge is stopped when the first layer region of the upper layer having a thickness of 3 μm is formed.
The gas flow into the deposition chamber 1001 was stopped by closing 2,1046 and the auxiliary valve 1018, and the formation of the first layer region of the upper layer was completed.

Next, to form the second layer region of the upper layer, the outflow valves 1041 and 1042 and the auxiliary valve 1018 are gradually opened and the SiH
_Four gases and H ₂ gas were introduced into the deposition chamber 1001 through the gas discharge holes 1009 of the gas introduction pipe 1008. At this time, the mass flow controllers 1021 and 1022 adjusted the SiH ₄ gas flow rate to 300 SCCM and the H ₂ gas flow rate to 300 SCCM. Deposition chamber 1
The opening of the main valve 1016 was adjusted while watching the vacuum gauge 1017 so that the pressure in 001 became 0.5 Torr. After that, the power of the RF power supply (not shown) was set to 15 mW / cm ³ and RF power was introduced into the deposition chamber 1001 through the high frequency matching box 1012,
An RF glow discharge is generated, a second layer region of the upper layer is formed on the first layer region of the upper layer, and an RF glow discharge is formed when the second layer region of the upper layer having a thickness of 20 μm is formed. Stop, and also set outflow valves 1041 and 1042 and auxiliary valve 1018
Was closed, the flow of gas into the deposition chamber 1001 was stopped, and the formation of the second layer region of the upper layer was completed.

Next, to form the third layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened and the SiH
_Four gases and CH ₄ gas were introduced into the deposition chamber 1001 through the gas discharge holes 1009 of the gas introduction pipe 1008. At this time, the flow rate of SiH ₄ gas is 50
SCCM, CH ₄ gas flow rate was adjusted with the corresponding mass flow controllers 1021,1023 such that 500 SCCM. Deposition chamber 1001
The opening of the main valve 1016 was adjusted while watching the vacuum gauge 1017 so that the internal pressure became 0.4 Torr. After that, the power of the RF power supply (not shown) was set to 10 mW / cm ³ and RF power was introduced into the deposition chamber 1001 through the high-frequency matching box 1012, and RF power was supplied.
Generate a glow discharge, start forming a third layer region on the second layer region of the upper layer, stop the RF glow discharge when the third layer region of the upper layer having a thickness of 0.5 μm is formed, Also, close the outflow valves 1041 and 1043 and the auxiliary valve 1018,
The flow of gas into the deposition chamber 1001 was stopped, and the formation of the third layer region of the upper layer was completed.

Table 1 shows the conditions for forming the light receiving member for electrophotography.

It goes without saying that the outflow valves other than the gas necessary for forming each layer are completely closed, and each gas is supplied to the inside of the deposition chamber 1001 and outflow valves 1041 to 1041.
To avoid remaining in the piping from 1047 to the deposition chamber 1001, the outflow valves 1041 to 1047 are closed and the auxiliary valve 10
Open 18 and then fully open the main valve to evacuate the system once to a high vacuum as needed.

During the layer formation, the cylindrical aluminum-based support 1005 is rotated at a desired speed by a driving device (not shown) in order to make the layer formation uniform.

<Comparative Example> When forming the lower layer, H ₂ gas, SiF ₄ gas, NO gas,
An electrophotographic light-receiving member was prepared under the same preparation conditions as in Example 1 except that ₂ H ₆ / H ₂ gas was not used.

Table 2 shows the conditions for forming the light receiving member for electrophotography.

The prepared electrophotographic light receiving members of Example 1 and Comparative Example were each set in an electrophotographic apparatus in which a copying machine NP-7550 made by Canon was modified for experiments, and several conditions were set under various conditions. When the electrophotographic characteristics were checked, no image defects were observed even when a high voltage was applied to the electrophotographic light-receiving member due to extremely strong corona charging and frictional charging due to a cleaning agent and the like. It has been found that it has a remarkable characteristic for withstand voltage.

Next, when the number of spots was compared as an image characteristic, in particular, the number of spots having a diameter of 0.1 mm or less was better for the electrophotographic light receiving member of Example 1 than for the electrophotographic light receiving member of Comparative Example.
It turned out that the number of spots was less than 1/2. Furthermore, in order to compare the degree of roughness, 100 points of image density were measured with a circular area having a diameter of 0.05 mm as one unit,
When the variation of the image density was evaluated, the variation of the electrophotographic light receiving member of Example 1 was 1/2 or less than that of the electrophotographic light receiving member of Comparative Example, and the electrophotographic light receiving member of Example 1 was visually observed. It was found that the light receiving member was superior to the electrophotographic light receiving member of the comparative example.

In addition, in order to compare the degree of occurrence of image defects and the occurrence of peeling of the light-receiving layer due to relatively short-term mechanical pressure applied to the light-receiving member for electrophotography, a diameter of 3.5 mm was used.
The stainless steel ball of Example 1 was dropped freely from 30 cm vertically above the surface of the electrophotographic light-receiving member and was applied to the surface of the electrophotographic light-receiving member, and the probability of cracks in the light-receiving layer was measured. It was found that the probability of occurrence of the photographic light receiving member was 2/5 or less of that of the electrophotographic light receiving member of the comparative example.

As can be seen from the above, the light receiving member for electrophotography of Example 1 was generally superior to the light receiving member for electrophotography of Comparative Example.

Example 2 In the lower layer of Example 1, AlCl was used without using NO gas.
The method of changing the ₃ / He gas flow rate was changed, and a light-receiving member for electrophotography was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 3, and the same evaluation was performed. In addition, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 3> A light receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 4 without using CH ₄ gas in Example 1, and the same evaluation was performed. As in the case of Example 1, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 4> In Example 1, He gas (purity 9) was supplied from a cylinder (not shown).
(9.9999%) was further used, and a light-receiving member for electrophotography was prepared in the same manner as in Example 1 under the conditions shown in Table 5, and the same evaluation was performed. A good effect of improving the peeling of the layer was obtained.

<Example 5> In Example 1 B ₂ H ₆ / H ₂ gas cylinder and abbreviated as PH ₃ gas (hereinafter PH ₃ / H ₂ gas diluted with hydrogen. 99.999
%) Cylinders and NO gas cylinders with NH ₃ gas (purity 99.99%
9%) A light receiving member for electrophotography was prepared in the same manner as in Example 1 under the conditions shown in Table 6 instead of the cylinder, and the same evaluation was carried out. A good effect of improving the peeling of the layer was obtained.

Further using C ₂ H ₂ gas from a cylinder (not shown) <Example 6> Example 1, the generating conditions shown in Table 7, was produced in the same manner the electrophotographic light-receiving member as in Example 1, the same As a result of the evaluation, as in the case of Example 1, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 7> A PH ₃ / H ² gas was further used from a cylinder (not shown), and a light receiving member for electrophotography was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 8, and the same evaluation was performed. As a result, similar effects to those of Example 1 were obtained, and a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 8> N ₂ gas from a cylinder (not shown), H ₂ S gas, the PH ₃ / H ₂ gas and further used in Example 1, the generating conditions shown in Table 9, the electron in the same manner as in Example 1 A photographic light-receiving member was prepared and evaluated in the same manner. As in Example 1, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 9> In Example 1, the CH ₄ gas cylinder was replaced with a C ₂ H ₂ gas (99.
9999%) Instead of a cylinder, a light receiving member for electrophotography was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 10,
As a result of a similar evaluation, a favorable effect of improving spotting, roughening, and layer peeling was obtained as in Example 1.

<Example 10> Example _{1, B 2 H 6 / H} 2 gas cylinder and abbreviated as BF ₃ gas (hereinafter BF ₃ / H ₂ gas diluted with hydrogen. 99.999
%) The light receiving member for electrophotography was changed in the same manner as in Example 1 under the conditions shown in Table 11 by changing the gas cylinder to a NO gas cylinder, changing the NO gas cylinder to an N ₂ gas cylinder, and using H ₂ S gas from a cylinder (not shown). Was prepared and the same evaluation was performed.
In the same manner as described above, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 11> In Example 1, the NO gas cylinder was replaced with NH ₃ gas (purity 99.99%).
9%) Instead of a cylinder, according to the preparation conditions shown in Table 12,
A light-receiving member for electrophotography was prepared in the same manner as in Example 1, and the same evaluation was performed. As in Example 1, a favorable effect of improving spotting, roughening, and peeling of the layer was obtained.

<Example 12> PF ₅ gas diluted with hydrogen from a cylinder (not shown)
Abbreviated as F ₅ / H ₂ gas. (Purity: 99.999%), PH ₃ / H ₂ gas was further used, the G ₂ H ₂ gas cylinder was changed to a CH ₄ gas cylinder, and the electrophotographic light-receiving member was manufactured in the same manner as in Example 6 under the preparation conditions shown in Table 13. It was prepared and evaluated in the same manner. As in Example 6, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 13> further using Si ₂ F ₆ gas from a cylinder (not shown), 14
Under the conditions shown in the table, a light-receiving member for electrophotography was prepared in the same manner as in Example 9 and the same evaluation was performed. As a result, similar to Example 9, spots, roughening, and layer peeling were improved. Effect was obtained.

<Example 14> A light receiving member for electrophotography was prepared in the same manner as in Example 11 by further using PH ₃ / H ₂ gas and Si ₂ F ₆ gas under the preparation conditions shown in Table 15, and evaluated similarly. As a result, as in Example 11, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

Example 15 In the upper layer, a GeH ₄ gas was further used from a cylinder (not shown), and under the conditions shown in Table 16, an electrophotographic light-receiving member was prepared in the same manner as in Example 1, and the same evaluation was performed. As a result, similar effects to those of Example 1 were obtained, and a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 16> In Example 1, the outer diameter of the cylindrical aluminum-based support was set to 80 mm, and a light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 17; The same evaluation as in Example 1 was conducted except that an electrophotographic apparatus modified from the copying machine NP-9030 for experiments was used. As a result, the same improvement as in Example 1 was obtained with respect to spotting, roughening, and layer peeling. Good effects were obtained.

<Example 17> In Example 1, the outer diameter of the cylindrical aluminum-based support was set to 60 mm, and a light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 18; The same evaluation as in Example 1 was performed except that an electrophotographic apparatus modified from the copying machine NP-150Z for experiments was used. As a result, the same improvement as in Example 1 was obtained with respect to spotting, roughening, and layer peeling. Good effects were obtained.

<Example 18> In Example 1, the outer diameter of the cylindrical aluminum-based support was set to 30 mm, and a light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 19, and was manufactured by Canon. The same evaluation as in Example 1 was performed except that an electrophotographic apparatus was used in which the copying machine FC-5 was modified for experiments.
In the same manner as described above, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 19> In Example 1, the outer diameter of the cylindrical aluminum-based support was set to 15 mm, and a light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 20. The same evaluation as in Example 1 was performed except that the electrophotographic apparatus prototyped in Example 1 was used.
A good effect of improving the peeling of the layer was obtained.

<Example 20> In Example 16, a mirror-finished cylindrical aluminum-based support was further machined by a sword tool,
An electrophotographic light-receiving member was prepared under the same conditions as in Example 16 using a cylindrical aluminum-based support having a sectional shape as shown in FIG. 38 and a = 25 μm and b = 0.8 μm.
The same evaluation as in Example 16 was carried out. As in Example 16, good effects of improving spotting, roughening, and layer peeling were obtained.

<Example 21> In Example 16, the mirror-finished cylindrical aluminum-based support was continuously exposed to a large number of bearing balls falling, and countless dents were formed on the surface of the cylindrical aluminum-based support. The surface is subjected to a so-called surface dimple treatment to produce c = 50 μm and d = 1 in a sectional shape as shown in FIG.
Example using a cylindrical aluminum-based support of μm
Create a light receiving member for electrophotography under the same conditions as 16
When the same evaluation as in Example 16 was performed, a favorable effect of improving spotting, roughening, and layer peeling was obtained as in Example 16.

<Example 22> In Example 9, the temperature of the cylindrical aluminum-based support was set to 500 ° C, and the photoreceptor for electrophotography in which the upper layer was made of poly-Si (H, X) under the preparation conditions shown in Table 21. A member was prepared in the same manner as in Example 9, and the same evaluation was performed. As in Example 9, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

Example 23 The light receiving member for electrophotography of the present invention was produced by a microwave (hereinafter abbreviated as “μW”) glow discharge decomposition method.

The deposition apparatus 1000 of the manufacturing apparatus of the RF glow discharge decomposition method shown in FIG. 37 was replaced with the deposition apparatus 1100 for the μW glow discharge decomposition method shown in FIG. 40 and connected to the raw material gas supply apparatus 1020.
An apparatus for manufacturing a light receiving member for electrophotography by the μW glow discharge decomposition method shown in FIG. 41 was used.

In the figure, reference numeral 1107 denotes a cylindrical aluminum-based support having an outer diameter of 108 mm and a mirror-finished surface.

First, as in Example 1, the inside of the deposition chamber 1101 and the gas pipe were evacuated until the pressure in the deposition chamber 1101 became 5 × 10 ⁻⁶ Torr.

Thereafter, as in Example 1, each gas was introduced into the mass flow controllers 1021 to 1027.

The temperature of the cylindrical aluminum-based support 1107 installed in the deposition chamber 1101 is controlled by a heater (not shown).
Heated to ° C.

After the preparation for the film formation was completed as described above, the lower layer and the upper layer were formed on the cylindrical aluminum-based support 1107. To form the lower layer, the outflow valve 104
1,1042,1044,1045,1046,1047 and auxiliary valve 1018 are gradually opened to release SiH ₄ gas, H ₂ gas, SiF ₄ gas, B ₂ H ₆ / H ₂ gas, NO gas, AlCl ₃ / He gas. The gas was introduced into the plasma generation region 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, the SiH ₄ gas flow rate was 150 SCCM, and the H ₂ gas flow rate was 20 S
Each mass flow controller has a CCM, SiF ₄ gas flow rate of 10 SCCM, a B ₂ H ₆ / H ₂ gas flow rate of 60 ppm with respect to the SiH ₄ gas flow rate, a NO gas flow rate of 10 SCCM, and an AlCl ₃ / He gas flow rate of 400 SCCM. The values were adjusted at 1021, 1022, 1024, 1025, 1026, and 1027. The opening of the main valve (not shown) was adjusted while watching the vacuum gauge (not shown) so that the pressure in the deposition chamber 1101 became 0.6 mTorr. Thereafter, the power of a μW power supply (not shown) was set to 0.5 W / cm ³ , and μW power was introduced into the plasma generation region 1109 through the waveguide 1103 and the dielectric window 1102 to generate a μW glow discharge, and the cylindrical aluminum The formation of the lower layer on the system support 1107 was started. During formation of the lower layer, SiH ₄ gas flow rate is 150SCC
As a constant flow rate of M, H ₂ gas flow rate from 20 SCCM 500
To increase at a constant rate in SCCM, SiF ₄ gas flow rate 10
The B ₂ H ₆ / H ₂ gas flow rate is SiH ₄ so that the SCCM flow rate is constant.
As a constant flow rate of 60ppm with respect to the gas flow, as NO gas flow rate to be constant flow rate of 10 SCCM, the AlCl ₃ / the He gas flow rate decreases at a constant rate 80SCCM from the support side 0.01μm in 400SCCM 80 SCCM at 0.01 μm on the upper layer side
The mass flow controllers 1021, 1022, 1024, 1025, 1026, and 1027 were adjusted so as to decrease at a fixed rate from 50 to 50 SCCM, and when the lower layer having a layer thickness of 0.02 μm was formed, the μW glow discharge was stopped. , 1042,1044,1045,
By closing 1046 and 1047 and the auxiliary valve 1018, the flow of gas into the plasma generation region 1109 was stopped, and the formation of the lower layer was completed.

Next, to form the first layer region of the upper layer, the outflow valve 1041, 1042, 1044, 1045, 1046, and the auxiliary valve 1018
Was gradually opened, and SiH ₄ gas, H ₂ gas, SiF ₄ gas, B ₂ H ₆ gas, and NO gas were caused to flow into the plasma generation space 1109 through gas discharge holes (not shown) of the gas introduction pipe 1110. At this time, Si
H ₄ gas flow rate is 350 SCCM, H ₂ gas flow rate is 350 SCCM, SiF ₄ gas flow rate is 20 SCCM, B ₂ H ₆ flow rate gas is 600 with respect to SiH ₄ gas flow rate
The mass flow controllers 1021, 1022, 1024, 1025, and 1026 were adjusted so that the ppm and NO gas flow rates became 13 SCCM.
The pressure in the deposition chamber 1101 was adjusted to be 0.5 mTorr. Thereafter, the power of a μW power supply (not shown) was set to 0.5 W / cm ³ to generate a μW glow discharge in the plasma generation chamber 1109 similarly to the lower layer, and the first layer region of the upper layer was formed on the lower layer. The formation was started, and a first layer region of an upper layer having a thickness of 3 μm was formed.

Next, in order to form the second layer region of the upper layer, the outflow valves 1041, 1042, 1044 and the auxiliary valve 1018 are gradually opened, and SiH ₄ gas, H ₂ gas, and SiF ₄ are connected to the gas introduction pipe 1110. The gas was allowed to flow into the plasma generation space 1109 through the illustrated gas discharge holes. At this time, the SiH ₄ gas flow rate was 700 SCCM, and the H ₂ gas flow rate was 500
The mass flow controllers 1021, 1022, and 1024 adjusted the SCCM and SiF ₄ gas flow rates to 30 SCCM. Deposition chamber 11
The pressure in 01 was adjusted to be 0.5 mTorr. Thereafter, the power of a μW power supply (not shown) was set to 0.5 W / cm ³ , and a μW glow discharge was generated in the plasma generation chamber 1109 similarly to the lower layer, and the upper layer was formed on the first layer region of the upper layer. Was started to form a second layer region of the upper layer having a thickness of 20 μm.

Next, to form the third layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened and the SiH
_Four gases and CH ₄ gas were introduced into the plasma generation space 1109 through gas discharge holes (not shown) of the gas introduction pipe 1110. At this time, the mass flow controllers 1021 and 1023 adjusted the flow rates of the SiH ₄ gas to 150 SCCM and the flow rate of the CH ₄ gas to 500 SCCM. The pressure in the deposition chamber 1101 was 0.3 mTorr. Thereafter, the power of a μW power supply (not shown) was set to 0.5 W / cm ³ to generate a μW glow discharge in the plasma generation region 1109, and a first layer of the upper layer having a layer pressure of 1 μm was formed on the second layer region of the upper layer. Three layer regions were formed.

Table 22 shows the conditions for preparing the electrophotographic light-receiving member described above.

The electrophotographic light-receiving member was evaluated in the same manner as in Example 1. As a result, similar effects to those in Example 1 were obtained, and a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 24> In Example 1, the CH ₄ gas cylinder was replaced with a C ₂ H ₂ gas (99.
9999%) An electrophotographic light-receiving member was prepared in the same manner as in Example 1 except that the cylinder was replaced with the preparation conditions shown in Table 23.
As a result of a similar evaluation, a favorable effect of improving spotting, roughening, and layer peeling was obtained as in Example 1.

The NO gas cylinder <Example 25> Example 1 instead of the N ₂ gas cylinder, the generating conditions shown in Table 24, to create the electrophotographic light-receiving member as in Example 1, was subjected to the same evaluation However, as in the case of Example 1, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

PF ₅ gas from a cylinder (not shown) <Example 26> Example 1, Si ₂ F ₆
Using gas, change NO gas cylinder to NH ₃ gas cylinder,
Under the conditions shown in Table 25, an electrophotographic light-receiving member was prepared in the same manner as in Example 1, and the same evaluation was performed.
As in the case of Example 1, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 27> The PF ₅ / H ₂ gas was further used from a cylinder (not shown),
According to the conditions shown in Table 6, a light-receiving member for electrophotography was prepared in the same manner as in Example 6, and the same evaluation was performed. As in Example 6, spots, roughening, and layer peeling were improved. Good effects were obtained.

<Example 28> Under the conditions shown in Table 27, a light-receiving member for electrophotography was prepared in the same manner as in Example 9, and the same evaluation was performed. As in Example 9, the spots, roughening, and layer peeling were observed. A good effect was obtained which was improved with respect to.

<Example 29> An electrophotographic light-receiving member was produced in the same manner as in Example 11 under the production conditions shown in Table 28 by further using PH ₃ / H ₂ gas, and the same evaluation was performed. As in the case of Example 11, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 30> In Example 1, He gas (purity) was supplied from a cylinder (not shown).
99.9999%), and a light-receiving member for electrophotography was prepared in the same manner as in Example 1 under the conditions shown in Table 29. The same evaluation was performed. As a result, a good effect of improving the layer peeling was obtained.

C ₂ H ₂ gas from a cylinder of <Example 31> (not shown), further using PH ₃ / H ₂ gas, by creating the conditions shown in Table 30, creating an electrophotographic light receiving member as in Example 1 When the same evaluation was performed, a good effect of improving spotting, roughening, and layer peeling was obtained as in Example 1.

<Example 32> PH ₃ / H ₂ gas was further used from a cylinder (not shown),
1. Under the conditions shown in Table 1, a light receiving member for electrophotography was prepared in the same manner as in Example 31, and the same evaluation was performed. As in Example 6, spots, roughening, and layer peeling were improved. Good effects were obtained.

Further using C ₂ H ₂ gas from a cylinder of <Example 33> (not shown), the generating conditions shown in Table 32, similarly to create a light-receiving member for electrophotography in Example 1, subjected to the same evaluation As a result, as in the case of Example 1, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

C ₂ H ₂ gas from a cylinder of <Example 34> (not shown), further using PH ₃ / H ₂ gas, by creating the conditions shown in Table 33, creating an electrophotographic light receiving member as in Example 33 When the same evaluation was performed, a good effect of improving spotting, roughening, and layer peeling was obtained as in Example 1.

<Example 35> further using unillustrated C ₂ H ₂ gas from the bomb, PH ₃ / H ₂ gas, H ₂ S gas, the generating conditions shown in Table 34, for electrophotography in the same manner as in Example 1 A light-receiving member was prepared and evaluated in the same manner. As in Example 1, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

Further using C ₂ H ₂ gas from a cylinder of <Example 36> (not shown), by creating the conditions shown in 35 Table similarly to create a light-receiving member for electrophotography in Example 9, subjected to the same evaluation As a result, as in the case of Example 9, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 37> Under the conditions shown in Table 36, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 38> Under the conditions shown in Table 37, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 39> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 using BF ₃ gas from a cylinder (not shown) under the preparation conditions shown in Table 38, and the same evaluation was performed. As in the case of Example 36, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 40> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 39, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 41> Under the conditions shown in Table 40, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 42> Under the conditions shown in Table 41, a light receiving member for electrophotography was prepared in the same manner as in Example 36, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 43> Under the conditions shown in Table 42, a light receiving member for electrophotography was prepared in the same manner as in Example 36, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 44> Under the conditions shown in Table 43, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 45> PH ₃ gas from a cylinder (not shown), Si ₂ F ₆ further using gas, by creating the conditions shown in 44 Table creates an electrophotographic light-receiving member as in Example 36, the same As a result of performing a good evaluation, a good effect of improving spotting, roughening, and layer peeling was obtained as in Example 36.

<Example 46> Under the conditions shown in Table 45, an electrophotographic light-receiving member was prepared in the same manner as in Example 45, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 47> further using H ₂ S gas from a cylinder (not shown), by creating the conditions shown in 46 Table creates an electrophotographic light-receiving member as in Example 36 was subjected to the same evaluation However, the embodiment
As in the case of 36, a good effect was obtained which was improved with respect to spotting, roughening, and layer peeling.

<Example 48> Under the conditions shown in Table 47, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was performed. As in Example 36, a spot, a rough layer, and a layer peeled off. A good effect was obtained which was improved with respect to.

<Example 49> Under the conditions shown in Table 48, a light receiving member for electrophotography was prepared in the same manner as in Example 36, and the same evaluation was carried out. A good effect was obtained which was improved with respect to.

<Example 50> An NH ₃ gas was further used from a cylinder (not shown), and under the conditions shown in Table 49, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was performed. ,Example
As in the case of 36, a good effect was obtained which was improved with respect to spotting, roughening, and layer peeling.

<Example 51> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 50 by further using N ₂ gas from a cylinder (not shown), and the same evaluation was performed. , Example 36
In the same manner as described above, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 52> Under the conditions shown in Table 51, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 53> Under the conditions shown in Table 52, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 54> Under the conditions shown in Table 53, an electrophotographic light-receiving member was prepared in the same manner as in Example 45, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 55> Under the conditions shown in Table 54, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was carried out. A good effect was obtained which was improved with respect to.

[Effects of the Invention] By having the electrophotographic light receiving member of the present invention have the specific layer configuration as described above, it is possible to solve all the problems in the conventional electrophotographic light receiving member made of A-Si. And exhibit particularly excellent electrical properties, optical properties, photoconductive properties, image properties, durability and use environment properties.

In particular, in the present invention, aluminum atoms (Al), silicon atoms (Si), and especially hydrogen atoms (H) are contained in the lower layer in a non-uniform distribution state in the layer thickness direction, so that the aluminum-based support is Injection of charge (photocarrier) between the upper layer and the upper layer is improved, and furthermore, the systematic and structural continuity of constituent elements between the aluminum-based support and the upper layer is improved. Image characteristics are improved, halftones are clearly produced, and high-quality images with high resolution can be stably and repeatedly obtained.

Furthermore, image defects occur due to the relatively short-time impact mechanical pressure applied to the electrophotographic light-receiving member, and non-Si
(H, X) Prevents peeling of film and improves durability,
Furthermore, the stress generated due to the difference in the coefficient of thermal expansion between the aluminum-based support and the non-Si (H, X) film is reduced, and the non-Si
Cracks and peeling of the (H, X) film can be prevented, and the yield in productivity can be improved.

In particular, in the present invention, a silicon atom (Si),
Compensation of dangling bonds such as aluminum atoms (Al)
Since a structurally more stable state can be obtained, a remarkable improvement in image characteristics such as roughness and spots, in combination with the effect due to the distribution of the aluminum atoms (Al), silicon atoms (Si), and hydrogen atoms (H). It has the characteristic of being seen.

Further, in the present invention, a layer region in contact with the lower layer in the upper layer contains at least one atom of carbon atoms (C), nitrogen atoms (N), and oxygen atoms (O), so that the layer of the upper layer The quality is improved, the durability against high voltage is improved, and the adhesion between the upper layer and the lower layer is further improved, so that image defects and non-Si (H, X)
The occurrence of peeling of the film is prevented, and the durability is improved.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram for explaining a layer configuration of an electrophotographic light receiving member of the present invention, and FIG. 2 is a schematic configuration diagram for explaining a layer configuration of a conventional electrophotographic light receiving member. 3 to 8 show an aluminum atom (Al), a halogen atom (X), an atom for adjusting durability (CNOc) and an atom for adjusting image quality (CNOc) contained in the lower layer, respectively. FIG. FIGS. 9 to 16 show silicon atoms (Si), hydrogen atoms (H), halogen atoms (X), durability-adjusting atoms (CNOc), and image quality contained in the lower layer, respectively. Explanatory drawing of the distribution state of atoms (Mc) for adjusting the temperature. FIGS. 17 to 36 show the conductivity controlling atoms (M), carbon atoms (C) and / or nitrogen atoms (N) and / or oxygen atoms (O), and germanium atoms contained in the upper layer, respectively. FIG. 37 is an explanatory view of a distribution state of (Ge) and / or tin atoms (Sn). FIG. 37 is an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography according to the present invention, and is a glow discharge using RF. FIG. 38 is a schematic explanatory view of a manufacturing apparatus according to the method, FIG. 38 is an enlarged view of a cross section of the aluminum-based support when the light-receiving member for electrophotography of the present invention is formed in a V-shape, FIG. 39 is an enlarged view of a cross section of the aluminum-based support when the surface of the aluminum-based support is subjected to a so-called dimple treatment when forming the electrophotographic light-receiving member of the present invention. FIG. 40 is an electrophotographic light-receiving member of the present invention. Microwave group to form the light receiving layer of the receiving member. FIG. 41 is a schematic explanatory view of a deposition apparatus using a low discharge method. FIG. 41 is an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography according to the present invention. FIG. 1 is a schematic explanatory view of a manufacturing apparatus according to the present invention. 1. With reference to FIG. 1, 100... The electrophotographic light-receiving member 101 of the present invention 101... An aluminum-based support 102... A light-receiving layer 103. 200: Conventional light receiving member for electrophotography 201: Aluminum-based support 202: Photosensitive layer made of A-Si 203: Free surface In FIG. 37, 1000: Deposition device by RF glow discharge decomposition method 1001 … Deposition chamber 1005… Cylindrical aluminum support 1008… Gas introduction pipe 1009… Gas discharge hole 1012… High frequency matching box 1014… Heater 1015… Leak valve 1016… Main valve 1017… Vacuum gauge 1018 Auxiliary valve 1020 Source gas supply device 1021-1027 Mass flow controller 1031-1037 Gas inflow valve 1041-1047 Gas outflow valve 1051-1057 Valve of source gas cylinder 1061-1067 ... pressure regulation Units 1071 to 1077 ... Gas cylinder for raw material 1078 ... Closed container for raw material In Fig. 40 and Fig. 41, 1100 ... Deposition device 1101 by microwave glow discharge method ... Deposition chamber 1102 ... Dielectric window 1103 ... Conductor Corrugated part 1107 cylindrical aluminum support 1109 plasma generation area 1010 gas introduction pipe

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location H01L 31/08 H01L 31/08 Q (72) Inventor Toshimitsu Kariya 3-30 Shimomaruko, Ota-ku, Tokyo 2. Canon Inc. (72) Inventor Hiroaki Shinno 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-59-28162 (JP, A)

Claims (1)

(57) [Claims] 1. A light-receiving member having an aluminum-based support and a light-receiving layer having a photoconductive multilayer structure on the support, wherein the light-receiving layer is at least an aluminum atom as a constituent element from the support side. And silicon atoms,
Periodic table excluding hydrogen atoms, halogen atoms, and aluminum atoms as atoms for adjusting image quality. Periodic table excluding aluminum group. III. Periodic table excluding nitrogen atom. Periodic table excluding oxygen belonging to group V. A lower layer composed of an inorganic material containing at least one selected from atoms belonging to Group VI, and a non-single-crystal material containing silicon atoms as a base and containing at least one selected from hydrogen atoms and halogen atoms And an upper layer containing at least one atom selected from a carbon atom (C), a nitrogen atom (N), and an oxygen atom (O) in a layer region in contact with the lower layer; In the layer, the content of the aluminum atoms in the lower layer is more than 5 atomic% and less than 95 atomic% by changing at least the introduction ratio of hydrogen gas. Has a portion containing in a non-uniform distribution state in the layer thickness direction such that the content decreases toward the upper layer, and the content of the silicon atoms and the hydrogen atoms in the lower layer is reduced toward the upper layer. A light-receiving member having a portion containing a non-uniform distribution in a layer thickness direction such that the content of hydrogen atoms is 0.01 atomic% or more and 70 atomic% or less.