JP2603264B2 - 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. Particularly, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used as an office machine in an office, the above-mentioned non-pollution during use is an important point.

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. The application as a photographic light receiving member is described.

FIG. 2 is a cross-sectional view schematically showing the layer structure of a conventional electrophotographic light-receiving member, wherein 201 is an aluminum-based support, and 202 is a photosensitive layer made of A-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 photosensitive layer 202 made of A-Si is formed by a film forming method such as a plasma CVD method, a sputtering method or the like.

However, in this light receiving member for electrophotography, since the thermal expansion coefficients of aluminum and A-Si are different by an order of magnitude, cracks and peeling may occur in the A-Si photosensitive layer 202 during cooling after film formation. It has become. In order to solve these problems, JP-A-59-28162 proposes an electrophotographic photoreceptor comprising an intermediate layer containing at least aluminum and an A-Si photosensitive layer on an aluminum-based support. In addition, the intermediate layer containing at least aluminum reduces stress generated due to a difference in thermal expansion coefficient between the aluminum-based support and the A-Si photosensitive layer, thereby reducing cracking and peeling of the A-Si photosensitive layer.

[Problems to be solved by the invention]

However, the conventional electrophotographic light-receiving member having a light-receiving layer composed of A-Si has electrical, optical and photoconductive properties such as dark resistance, photosensitivity and photoresponsiveness, and use environment properties. However, in terms of stability over time and durability, the characteristics of each have been individually improved,
In fact, there is room for further improvement in overall improvement of characteristics.

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 have been problems such as the occurrence of image defects due to the mechanical pressure of the impact applied for a relatively short period of time and the peeling of the A-Si film, thereby impairing the durability of the light receiving member for electrophotography.

Further, there is a problem that cracks and peeling occur in the A-Si film due to stress generated due to a difference in coefficient of thermal expansion between the aluminum-based support and the A-Si film, and the yield in productivity is reduced.

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 as to solve all the above-mentioned problems. There is a need to make improvements from a strategic point of view.

[Means and actions for solving the problems]

The light receiving member for electrophotography of the present invention is an electrophotographic light receiving member having an aluminum-based support and a light receiving layer having a multilayer structure having at least photoconductivity on the support, wherein the light receiving layer is From the support side, at least aluminum atoms (A1) and silicon atoms (S
i), an inorganic material containing a hydrogen atom (H) and a magnesium atom (Mg) (hereinafter abbreviated as “A1SiH”), and the aluminum atom (A1), the silicon atom (Si) and the hydrogen atom (H) A lower layer having a portion containing a non-uniform distribution in the layer thickness direction, and containing at least one of a hydrogen atom (H) and a halogen atom (X) based on silicon atoms (Si) Non-crystalline material (hereinafter abbreviated as “A-Si (H, X)”. Materials commonly called microcrystalline material are classified as A-Si (H, X)) or polycrystalline material (Hereinafter abbreviated as "poly-Si (H, X)")
Alternatively, a so-called non-single crystalline material containing both (hereinafter referred to as “No.
n-Si (H, X) ") and an upper layer containing atoms (M) for controlling conductivity in a layer region in contact with the lower layer.

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.

In particular, by containing aluminum atoms (A1) and silicon atoms (Si), particularly hydrogen atoms (H) in the lower layer in a non-uniform distribution state in the layer thickness direction, the distance between the aluminum-based support and the upper layer is increased. In addition, since the injection property of the electric charge (photo carrier) in the substrate is improved, and the systematic and structural continuity of the constituent elements between the aluminum-based support and the upper layer is improved, the image characteristics such as roughness and spots are improved. And a high-quality image with a clear halftone and high resolution can be repeatedly obtained stably.

Furthermore, image defects are generated due to relatively short-time mechanical pressure applied to the light receiving member for electrophotography, and Non-S
Prevents peeling of the i (H, X) 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, as a distinctive feature of the lower layer containing magnesium atoms (Mg), the injection and adhesion of electric charge (photocarrier) between the aluminum-based support and the upper layer and the lower layer. Since the traveling property of the electric charge (photocarrier) in the layer is remarkably improved, there is a feature that a remarkable improvement in image characteristics and durability is observed.

Further, in the present invention, by injecting atoms (M) for controlling conductivity into a layer region in contact with the lower layer in the upper layer, charge injection or charge injection between the upper layer and the lower layer is prevented. Can be selectively controlled or improved, image characteristics such as roughness and spots are improved, halftones are clearly output, and high resolution, high quality images can be repeatedly obtained stably. Charging ability, sensitivity and durability are also improved.

JP-A-59-28162 mentions that aluminum atoms (A1) and silicon atoms (Si) are non-uniformly contained in the layer thickness direction, and that hydrogen atoms (H) are contained. However, it does not mention how the hydrogen atom (H) is 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 A1SiH on an aluminum-based support 101 for an electrophotographic light-receiving member, and the aluminum atom (A1)
Layer 103 having a portion containing silicon, silicon atoms (Si) and hydrogen atoms (H) in a non-uniform distribution state in the layer thickness direction.
And a light receiving layer 102 having a layer structure comprising: Non-Si (H, X); and an upper layer 104 containing atoms (M) for controlling conductivity in a layer region in contact with the lower layer. Having.

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, A1-Cu, A1-Mn,
Alloys with compositions such as A1-Si, A1-Mg, A1-Mg-Si, A1-Zn-Mg, etc., A1-Cu-Mg (Duralumin, super duralumin, etc.), A1-Cu-Si (Lautar, etc.), A1-Cu-Ni
-Mg type (Y alloy, RR alloy, etc.), aluminum powder sintered body (SAP), etc. are contained.

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 pure aluminum include, for example, JIS1100, Si and Fe 1.0% by weight or less, Cu 0.05 to 0.20% by weight, Mn 0.05% by weight or less, Zn 0.10% by weight or less, and A199.00% by weight or more. .

As an A1-Cu-Mg system, for example, JIS2017, Si0.05 ~
0.20 wt%, Fe 0.7 wt% or less, Cu 3.5-4.5 wt%, Mn
0.40 to 1.0% by weight, Mg 0.40 to 0.8% by weight, Zn 0.25% by weight or less, Cr 0.10% by weight or less, and the balance of A1.

As the A1-Mn system, 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, Mu 1.0 to 1.
5% by weight, Zn 0.10% by weight or less, and the balance of A1.

Examples of the A1-Si system include, for example, JIS4032, Si11.0 to 13.5 wt%, Fe1.0 wt% or less, Cu0.50 to 1.3 wt%, Mg0.8 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 A1.

As an A1-Mg system, for example, JIS5086, SI 0.40% by weight or less, Fe 0.50% by weight or less, Cu 0.10% by weight or less, Mn 0.20-0.
7 wt%, Mg 3.5-4.5 wt%, Zn 0.25 wt% or less, Cr0.0
5 to 0.25% by weight, Ti 0.15% by weight or less, and the balance of A1.

Furthermore, Si 0.50% by weight or less, Fe 0.25% by weight or less, Cu
0.04 to 0.20% by weight, Mn 0.01 to 1.0% by weight, Mg 0.5 to 10% by weight, Zn 0.03 to 0.25% by weight, Cr 0.05 to 0.50% by weight, Ti or
Zr0.05~0.20 wt%, 1.0 cc or less with respect to H ₂ A1 100 grams, include A1 balance.

Further, Si 0.12% by weight or less, Fe 0.15% by weight or less,
0.30 wt% or less of Mn, 0.5 to 5.5 wt% of Mg, 0.01 to 1.0 wt% of Zn, 0.20 wt% or less of Cr, 0.01 to 0.25 wt% of Zr, and the balance of A1.

A1-Mg-Si based, for example, JIS6063, Si0.20 ~
0.6% by weight, Fe 0.35% by weight or less, Cu 0.10% by weight 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 remainder of A1.

As the A1-Zn-Mg system, for example, JIS7N01, Si0.30% by weight or less, Fe0.35% by weight or less, Cu0.20% by weight or less, Mn0.
20-0.7 wt%, Mg1.0-2.0 wt%, Zn4.0-5.0 wt%, Cr0.30 wt% or less, Ti0.20 wt% or less, Zr0.25 wt% or less, V0.10 wt% or less, A1 remainder.

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, in the case of precision machining accompanied by mirror-cutting, etc., magnesium (Mg) and / or The coexistence of copper (Cu) improves the free-cutting properties of the aluminum alloy.

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 a so-called interference fringe pattern 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 depressions provided on the surface of the support are prepared by a known method described in JP-A-61-231561.

Lower Layer The lower layer in the present invention is made of an inorganic material containing at least aluminum atoms (A1), silicon atoms (Si), hydrogen atoms (H), and magnesium atoms (Mg) as components, and has durability as required. The atom that regulates (CNO _c ),
It may contain atoms (M _c ), halogen atoms (X), germanium atoms (Ge), and tin atoms (Sn) for adjusting image quality.

Aluminum atoms (A1), 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.

Magnesium atoms (Mg) contained in the lower layer, germanium atoms (Ge) and tin atoms (Sn) contained as needed, atoms for adjusting durability (CNO _c ), and atoms for adjusting image quality ( M _c ) and a halogen atom (X)
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.

Further, in one of the preferred embodiments, an aluminum atom (A1) and a silicon atom (S
i) The distribution of hydrogen atoms (H) is as follows: aluminum atoms (A1), silicon atoms (Si), hydrogen atoms (H)
Is distributed continuously and without unevenness, and the distribution concentration of aluminum atoms (A1) 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, the aluminum atom (A1) 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.
1), magnesium atom (Mg), and germanium atom (Ge) and tin atom (Sn) which are contained as needed, atoms for adjusting durability (CNO _c ) and atoms for adjusting image quality (M _c ) and A typical example of a distribution state of a halogen atom (X) in a layer thickness direction is shown.

3 to 8, the horizontal axis represents an aluminum atom (A1) (hereinafter abbreviated as "atom (A1)"), a magnesium atom (Mg) (hereinafter abbreviated as "atom (Mg)"), and a germanium atom. (Ge) and tin atom (Sn) (hereinafter abbreviated as “atom (GS _c )”), atoms that adjust durability (CN
O _c ) (hereinafter abbreviated as “atom (CNO _c )”), an atom for adjusting image quality (M _c ) (hereinafter abbreviated as “atom (M _c )”), a halogen atom (X) (hereinafter abbreviated as “atom ( _C abbreviated to X) ", atom (A1) and atom and (Mg) atom and (GS _c) atom and (CNO _c) atom and (M _c) atom (X) are collectively referred to as" atoms (AM) " abbreviated. However the layer thickness direction of the distribution of atoms (A1) and atoms (Mg) and atoms (GS _c) and atoms (CNO _c) and atoms (M _c) and atoms (X) may be the same distribution concentration C of and may be different), 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 is the position of the end face of the lower layer of the upper layer side Is shown. That is, the lower layer containing atoms (AM)
It is a layer formed toward the t _T side from t _B side.

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

In the example shown in FIG. 3, the distribution concentration C of the atoms contained (AM) 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 (AM) 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 (AM) gradually and continuously decreases 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 (AM) 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.

In the example shown in FIG. 7, the distribution concentration C of the atoms contained (AM) is up to the position t ₇₁ from the position t _B takes a constant value consisting concentration C _71, reaches the position t _T to the position t ₇₁ gradually decreases continuously from the concentration C ₇₂ to form a kind of distribution that the concentration C ₇₃ at position t _T.

In the example shown in FIG. 8, the distribution concentration C of the atoms contained (AM) gradually and continuously decreases from the concentration C ₈₁ up to the position t _T to the position t _B, the concentration at position t _T forming a kind of distribution becomes C _82.

As described above, some of the typical examples of the distribution state of the atoms (A1) 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 (A1), 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 (A1) 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 the atom (A1) 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;
Hydrogen atom (H), magnesium atom (Mg), germanium atom (Ge) and tin atom (Sn), atom (CNO _c ), atom (M _c ), halogen atom (X) A typical example of the distribution state in the layer thickness direction is shown.

9 to 16, the horizontal axis is the silicon atom (S
i), hydrogen atom (H), magnesium atom (Mg), atom (GS _c ), atom (CNO _c ), atom (M _c ), atom (X) (hereinafter collectively referred to as “atom (SHM)”) Where silicon atoms (Si), hydrogen atoms (H), magnesium atoms (Mg), atoms (GS _c ), atoms (CNO _c ), atoms (M _c ), and atoms (X) in the layer thickness direction. distribution concentration C of the distribution may be different may be the same), 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 the top The position of the end face of the lower layer on the layer side is shown. That is, the lower layer contained the atoms (SHM) is a layer formed toward the t _T side from t _B side.

FIG. 9 shows a first typical example of the distribution state of atoms (SHM) 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 (SHM) temporarily increases from the concentration C ₉₁ from the position t _B to the position t ₉₁ , and then increases from the position t ₉₁ to the position t _91. 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 (SHM) 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 (SHM), 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 of the contained atoms (SHM) is the concentration C ₁₂₁ from the position t _B to the position t _121.
Next concentration C ₁₂₂ at position t ₁₂₁ increases temporarily functionally from to a position t _T to the position t ₁₂₁ 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 of the contained atoms (SHM) is the concentration C ₁₃₁ from the position t _B to the position t _131.
And gradually increases from the concentration C ₁₃₂ at the position t ₁₃₁ .
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 (SHM) 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 (SHM) is substantially zero (below the detection limit amount substantially zero here up to the position t ₁₅₁ to the position t _B The same applies to the meaning of “substantially zero” hereinafter), and the density gradually increases to the density C ₁₅₁ at the position t ₁₅₁ , and the position t ₁₅₁
Forming a kind of distribution takes a constant value consisting concentration C ₁₅₂ up to the position t _T than _151.

In the example shown in FIG. 16, the distribution concentration C of the atoms contained (SHM) is 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 (A1), and a silicon atom (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%.

In the present invention, magnesium atoms (Mg)
To improve the charge injection property between the aluminum-based support and the upper layer and / or the effect of improving the charge transportability in the lower layer, and / or the aluminum-based support and the upper layer. The effect of improving the adhesion between the layers can be obtained.
The content of magnesium atoms (Mg) 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 2 × 10 ⁵
Atomic ppm, more preferably 1 × 10 ² to 1 × 10 ⁵ atomic ppm, and most preferably 5 × 10 ^{2 to} 5 × 10 ⁴ atomic ppm.

By containing germanium atoms (Ge) and / or tin atoms (Sn) in the lower layer contained as required, the effect of improving the charge injection property mainly between the aluminum-based support and the upper layer is improved. And / or an effect of improving charge transportability in the lower layer and / or
Alternatively, the effect of improving the adhesion between the aluminum-based support and the upper layer can be obtained. Further, the lower layer has an effect of narrowing the forbidden band width in a layer region where the content of aluminum atoms (A1) is small, and when a long-wavelength light such as a semiconductor laser is used as an image exposure source of an electrophotographic apparatus, an interference phenomenon occurs. The effect of reducing appearance can be obtained. The content of germanium atoms (Ge) and / or tin atoms (Sn) contained in the lower layer is appropriately determined as desired so as to effectively achieve the object of the present invention. 9 × 10 ⁵ atomic ppm, more preferably 1 × 10 ² to 8 × 10 ⁵ atomic ppm, and most preferably 5 × 10 ^{2 to} 7 ×
10 ⁵ desirably are atomic ppm.

As the halogen atom (X) contained as required, a fluorine atom (F), a chlorine atom (C1), 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 (C1) and / or a bromine atom (Br) and / or an iodine atom (I) as a halogen atom (X). Uncombined bonds such as silicon atoms (Si) and aluminum atoms (A1) mainly contained in the lower layer can be compensated, and the structure can be structurally stabilized to improve the layer quality. 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, it is 10 to ³ × 10 ⁵ atomic ppm, and most preferably, 1 × 10 ² to 2 × 10 ⁵ atomic ppm.

The atoms (CNO _c ) for adjusting the durability contained as necessary include carbon atoms (C), nitrogen atoms (N),
An oxygen atom (O) is used. In the present invention, the lower layer mainly contains an aluminum-based support by containing a carbon atom (C) and / or a nitrogen atom (N) and / or an oxygen atom (O) as atoms for adjusting durability (CNO _c ). The effect of improving the charge injectability between the body and the upper layer and / or the effect of improving the charge transportability in the lower layer and / or the effect of improving the adhesion between the aluminum-based support and the upper layer. Obtainable. Further, the effect of controlling the forbidden band width can be obtained in a layer region where the content of aluminum atoms (A1) is small in the lower layer. The atoms that adjust the durability contained in the lower layer (CN
The content of O _c ) is preferably 10 to 5 × 10 ⁵ atomic ppm,
More preferably, 5 × 10 ¹ to 4 × 10 ⁵ atomic ppm, optimally 1
Desirably, the concentration is from × 10 ^{2 to} 3 × 10 ⁵ atomic ppm.

As the atoms for adjusting the image quality contained as necessary (M _c ), atoms belonging to Group III of the periodic table excluding the aluminum atom (A1) (hereinafter abbreviated as “Group III atoms”), Atoms belonging to Group V of the periodic table except nitrogen atoms (N) (hereinafter abbreviated as “Group V atoms”), oxygen atoms (O)
And atoms belonging to Group VI of the periodic table (hereinafter abbreviated as "Group VI atoms"). Specific examples of Group III atoms include B (boron), Ga (gallium), In (indium), and T1 (thallium), with B and Ga being particularly preferred. Specific examples of Group V atoms include P (phosphorus), As
(Arsenic), Sb (antimony), Bi (bismuth), etc.
Particularly, P and As are preferable. 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, an atom (M _c ) for adjusting the image quality is provided in the lower layer as II
By containing a Group I atom, a Group V 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
Alternatively, the effect of improving the traveling property of the electric charge in the lower layer can be obtained. Furthermore, in the layer region where the content of aluminum atoms (A1) is small in the lower layer, the effect of controlling the conductivity type and / or conductivity can be obtained. The content of atoms (M _c ) 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 × 10 ⁴ atomic ppm. , Optimally 1 × 10 ^{-1 to} 5 ×
10 ³ desirably are atomic ppm.

In the present invention, the lower layer made of A1SiH is created, for example, by the same vacuum deposition film forming method as the upper layer described later, by appropriately setting numerical conditions of 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
-CVD, sputtering, vacuum deposition, ion plating, photo-CVD, active species (A) generated by decomposing a material gas, and chemical interaction with the active 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 source gas of a material and a halogen-based oxidizing gas having a property of oxidizing the source gas are separately introduced into a film forming section for forming a deposited film. Method of forming a material by chemically reacting them (hereinafter referred to as “FOCV
Abbreviated as "D method"). These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the electrophotographic light-receiving member to be produced. It is relatively easy to control the conditions for producing electrophotographic light-receiving members having characteristics, and it is easy to introduce hydrogen atoms (H) together with aluminum atoms (A1) and silicon atoms (Si). From the viewpoint of obtaining, etc., the glow discharge method, the sputtering method, the ion plating method, the HRCVD method, and the FOCVD method are preferable. These methods may be used together in the same apparatus system.

For example, to form a lower layer composed of A1SiH by a glow discharge method, basically, an A1 supply gas capable of supplying aluminum atoms (A1) and a silicon atom (S
i) a gas for supplying Si that can supply hydrogen, a gas for supplying H that can supply hydrogen atoms (H), a gas for supplying Mg that can supply magnesium atoms (Mg), and, if necessary, germanium atoms (Ge ) And tin atoms (Sn), a gas for supplying GS _c , a gas for supplying X that can supply halogen atoms (X) if necessary, and an atom (CNO _c for adjusting durability) as necessary. ) and CNO _c-feeding gas capable of supplying, the M _c-feeding gas capable of feeding atom (M _c) to adjust the image quality as required by the desired gas pressure conditions in the deposition chamber the inside can be a vacuum To generate a glow discharge in the deposition chamber, and onto a predetermined support surface previously set at a predetermined position.
What is necessary is just to form the layer which consists of A1SiH.

In order to form the lower layer composed of A1SiH by the HRCVD method, basically, an A1 supply gas that can supply aluminum atoms (A1) and a Si that can supply silicon atoms (Si)
Supply gas and Mg that can supply magnesium atoms (Mg)
A supply gas, a GS _c supply gas that can supply germanium atoms (Ge) and tin atoms (Sn) as needed, and an X supply gas that can supply halogen atoms (X) as needed. and CNO _c-feeding gas capable of feeding atom (CNO _c) to adjust the durability as required, the M _c-feeding gas capable of feeding atom (M _c) to adjust the image quality as necessary, should The glow discharge is generated in the activation space by introducing the glow discharge into the activation space separately or together with a desired gas pressure state into the activation space provided in the preceding stage in the deposition chamber, which can reduce the pressure inside. To generate an active species (A), and an H supply gas capable of supplying hydrogen atoms (H) is similarly introduced into another activation space to generate an active species (B). (A)
And the active species (B) may be separately introduced into the deposition chamber, and a layer made of A1SiH may be formed on the surface of a predetermined support previously set at a predetermined position.

In order to form the lower layer composed of A1SiH by FOCVD method, it can basically supply aluminum atoms (A1)
A1 supply gas, Si supply gas capable of supplying silicon atoms (Si), H supply gas capable of supplying hydrogen atoms (H), and Mg supply gas capable of supplying magnesium atoms (Mg) A GS _c supply gas that can supply germanium atoms (Ge) and tin atoms (Sn) as needed, an X supply gas that can supply halogen atoms (X) as needed, CN that can supply atoms (CNO _c ) to adjust durability
The O _c supply gas and the M _c supply gas, which can supply atoms (M _c ) for adjusting the image quality as needed, are separately or together as needed into a deposition chamber where the inside can be depressurized. Introduced at a desired gas pressure state, further introduced a halogen (X) gas into the deposition chamber separately from the source gas at a desired gas pressure state, and chemically reacted with these gases in the deposition chamber;
What is necessary is just to form a layer made of A1SiH on the surface of a predetermined support which is previously set at a predetermined position.

When formed by the sputtering method, for example, Ar,
Use a target composed of A1, a target composed of Si, or a target composed of A1 and Si in an atmosphere of an inert gas such as He or a mixed gas based on these gases. Then, an H supply gas capable of supplying hydrogen atoms (H), a Mg supply gas capable of supplying magnesium atoms (Mg), and a germanium atom (G
e) and a GS _c supply gas capable of supplying tin atoms (Sn), an X supply gas capable of supplying halogen atoms (X) if necessary, and an atom (CN for adjusting durability as necessary)
A CNO _c supply gas capable of supplying O _c ) and a M _c supply gas capable of supplying atoms (M _c ) for adjusting the image quality as necessary are introduced into a deposition chamber for sputtering, and further necessary. Accordingly, an A1 supply gas that can supply aluminum atoms (A1) and / or a Si supply gas that can supply silicon atoms (Si) are introduced into a deposition chamber for sputtering, and a plasma atmosphere of a desired gas is introduced. It is done by forming.

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 (A1), silicon atoms (Si), hydrogen atoms (H), and magnesium atoms (Mg) contained in the lower layer, and germanium contained as necessary Atom (Ge) and tin atom (S
n) and the distribution concentration C of halogen atoms (X), atoms for adjusting durability (CNO _c ), and atoms for adjusting image quality (M _c ) (hereinafter these are collectively abbreviated as “atom (ASH)”). In the case of the glow discharge method, the HRCVD method, and the FOCVD method, the distribution concentration should be changed in order to form a layer having a desired distribution profile (depth profile) in the layer thickness direction by changing This is achieved by introducing an atomic (ASH) supply gas 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.

As another method, the flow rate setting of the mass flow controller controlling the gas flow rate is appropriately changed by any method usually used such as manual or using a programmable controller.

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, if a sputtering target, for example, a mixed target of A1 and Si is used, the mixing ratio of A1 and Si is changed in advance in the thickness direction of the target. Is done.

It can be effectively used as a material and A1 supplying gas used in the present _{invention, A1C1 3, A1Br 3, A1I} 3, A1 (CH 3) 2 C1, A1 (C
_{H 3) 3, A1 (OCH} 3) 3, A1 (C 2 H 5) 3, A1 (OC 2 H 5) 3, A1 (iC 4 H 9)
₃ , A1 (iC ₃ H ₇ ) ₃ , A1 (C ₃ H ₇ ) ₃ , A1 (OC ₄ H ₉ ) _{3 and the} like can be used effectively. Further, these A1 supply gases may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

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 terms of ease of handling at the time of forming a layer and good Si supply efficiency. Further, these Si supply gases may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

The substance that can be a hydrogen supply gas used in the present invention is H ₂ , or SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , or Si ₄ H
Silicon hydrides (silanes) such as ₁₀ are effectively used.

In the present invention, the amount of hydrogen atoms contained in the lower layer can be controlled, for example, by controlling the flow rate of the raw material gas for supplying hydrogen or / and the temperature of the support or / and the discharge power. .

In order to structurally introduce magnesium atoms (Mg) into the lower layer, a raw material for supplying magnesium atoms (Mg) is formed in a gaseous state in the deposition chamber during the formation of the layer. What is necessary is just to introduce with other raw material. As a material that can be a raw material for supplying magnesium atoms (Mg), a material that is gaseous at normal temperature and normal pressure or that can be easily gasified at least under layer forming conditions is preferably used.

Substances that can be used as the Mg supply gas include organic metals containing magnesium atoms (Mg) that can be effectively used. Particularly, in terms of ease of handling during layer formation work and good Mg supply efficiency. And bis (cyclopentadienyl) magnesium (II) complex salt (Mg (C ₅ H ₅ ) ₂ ).

In addition, these Mg supply gases may be replaced with H ₂ , He,
It may be diluted with a gas such as r or He before use.

In order to structurally introduce germanium atoms (Ge) or tin atoms (Sn) into the lower layer, a source material for supplying germanium atoms (Ge) or a source material for supplying tin atoms (Sn) during layer formation. The raw material may be introduced in a gaseous state into the deposition chamber together with other raw materials for forming the lower layer. As a raw material for supplying germanium atoms (Ge) or a raw material for supplying tin atoms (Sn), those which can be gaseous at ordinary temperature and pressure or which can be easily gasified at least under layer forming conditions can be used. It is desirable to be adopted.

GeH ₄ , Ge
_{2 H 6, Ge 3 H 8} , Ge 4 H gaseous state, such as ₁₀ or the like as germanium hydride can be gasified is effectively used, in particular the layer created when working easy handling, Ge supply efficiency GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferable in terms of, for example, the quality of the film.

In addition, GeHF ₃ , GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ C
_{l 2, GeH 3 Cl, GeHBr} 3, GeH 2 Br 2, GeH 3 Br, GeHI 3, GeH
Germanium hydride such as ₂ I ₂ , GeH ₃ I, GeF ₄ ,
Materials in the gaseous state or gasifiable substances such as germanium halides such as GeCl ₄ , GeBr ₄ , GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , and GeI ₂ can also be mentioned as effective starting materials for forming the lower layer. .

Substances that can be Sn supply gas include SnH ₄ , Sn
It cited _{as 2 H 6, Sn 3 H 8} , Sn 4 tin hydride which may or gasified gas conditions such as H ₁₀ is effectively used,
In particular, SnH ₄ , Sn ₂ H ₆ , and Sn ₃ H ₈ are preferred in terms of ease of handling during layer formation work and high Sn supply efficiency.

In addition, SnHF ₃ , SnH ₂ F ₂ , SnH ₃ F, SnHCl ₃ , SnH ₂ Cl ₂ , S
nH ₃ Cl, SnHBr ₃ , SnH ₂ Br ₂ , SnH ₃ Br, SnHI ₃ , SnH ₂ I ₂ , SnH
Tin halides such as ₃ I, SnF ₄ , SnCl ₄ , SnBr ₄ , Sn
Substances in the gaseous state or gasifiable substances such as tin halides such as I ₄ , SnF ₂ , SnCl ₂ , SnBr ₂ and SnI ₂ can also be mentioned as effective starting materials for forming the lower layer.

Further, these GS _c supply gases may be replaced with H ₂ , He, A
It may be diluted with a gas such as r or Ne before use.

In order to structurally introduce a halogen atom (X) into the lower layer, a raw material for supplying the halogen atom (X) is formed in a gas state in the deposition chamber to form the lower layer during the formation of the layer. Should be introduced together with other raw materials. Effective as the halogen supply gas used in the present invention,
Many halogen compounds can be mentioned, for example, halogen compounds in gaseous state or gasizable such as halogen gas, halide, interhalogen compound, and silane derivative substituted with halogen.

Further, in the present invention, a silicon hydride compound containing a halogen atom, which is a gas state or can be gasified, which contains 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 , I
Interhalogen compounds such as Br can be mentioned.

As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ are preferable. .

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, a lower layer made of A1SiH containing a halogen atom can be formed on a desired support.

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, Si
H ₂ F ₂ , SiHF ₃ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiH
Halogen-substituted silicon hydrides such as Br ₃ , and other gaseous or gasifiable substances can also be mentioned as effective starting materials for forming the lower layer.

In the lower layer, there are atoms for adjusting the image quality (M _c ), 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 raw material for supplying Group III atoms, the raw material for supplying Group V atoms, or the raw material for supplying Group VI atoms may be gaseous at room temperature and normal pressure, or at least under conditions of layer formation. It is desirable to employ a material which can be easily gasified. As such a raw material for supplying Group III atoms, specifically, for supplying boron atoms, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B _{6 6} H ₁₂ ,
Examples thereof include boron hydrides such as B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ and BBr ₃ . In addition, CaCl ₃ , Ca (CH ₃ ) ₃ , InC
l ₃ , TlCl _{3 and the} like can also be mentioned.

As a raw material for supplying group V atoms, the present invention effectively uses PH ₃ , P for supplying phosphorus atoms.
₂ H _4, etc. of hydrogen phosphorus _{halides, PH 4 I, PF 3,} PF 5, PCl 3, PCl 5, PB
phosphorus halides such as r ₃ , PBr ₅ and PI ₃ ; In _{addition, AsH 3, AsF 3, AsCl} 3, AsBr 3, AsF 5, SbH 3, SbF 3, Sb
F ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for supplying Group V atoms.

As a raw material for supplying Group VI atoms, 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
Substances in the gaseous state or capable of being gasified, such as ₄ H ₄ S, (CH ₃ ) ₂ S, and (C ₂ H ₅ ) ₂ S, are mentioned. In addition, SeH ₂ , SeF ₆ , (CH ₃ ) ₂
Substances in a gaseous state or capable of being gasified, such as Se, (C ₂ H ₅ ) ₂ Se, TeH ₂ , TeF ₆ , (CH ₃ ) ₂ Te, and (C ₂ H ₅ ) ₂ Te.

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

In order to structurally introduce durability-adjusting atoms (CNO _c ) into the lower layer, for example, carbon atoms (C), nitrogen atoms (N), or oxygen atoms (O), carbon atoms must be formed during layer formation. (C) a source material for supply, a source material for supply of nitrogen atoms (N) or a source material for supply 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. The raw material for supplying carbon atoms (C), the raw material for supplying nitrogen atoms (N), or the raw material for supplying 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 carbon atom (C) supply gas include C and H as constituent atoms, for example, a saturated hydrocarbon having 1 to 4 carbon atoms, ethylene having 2 to 4 carbon atoms. 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 _10), 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 ).

In addition, CF ₄ , CCl ₄ , CH ₃ can be supplied in addition to the supply of hydrocarbons (C), because halogen atoms (X) can be supplied.
Halocarbon gases CF ₃ and the like.

Starting materials that are effectively used as potential nitrogen atom (N) supply gases include N as a constituent atom, or N and H as constituent atoms such as nitrogen (N ₂ ) and ammonia (NH ₃ ). ), Hydrazine (H ₂ NNH ₂ ), hydrogen azide (H
Examples include gaseous or gasifiable nitrogen such as N ₃ ) and ammonium (NH ₄ N ₃ ), and nitrogen compounds such as nitrogen and azide. In addition to this, in addition to the supply of nitrogen atoms (N), the supply of halogen atoms (X) can be performed, so that nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), etc. Nitrogen halide compounds can be mentioned.

Starting materials that are effectively used as potential oxygen atom (O) supply gases include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), 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 ), nitrogen trioxide (N
O ₃ ), for example, disiloxane (H ₃ Si) having silicon atom (Si), oxygen atom (O), and hydrogen atom (H) as constituent atoms.
OSiH ₃ ) and lower siloxanes such as trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ).

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 (A1) of the lower layer.
Is a region where the content of aluminum is 95% or less of the content of aluminum atoms (A1) in the aluminum-based support. This means that the aluminum atom (A1) content is 95% of the aluminum atom (A1) 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 (A1) in the lower layer exceeds 5%. This is because, in the region of the composition in which the content of the aluminum atom (A1) is 5% or less, the function almost has only the function of the upper layer.

In order to form a lower layer made of A1SiH 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, if 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, optimally and 1 × 10 ^-4 ~1Torr Is preferred.

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 40 ° C.
Desirably, it is 0 ° 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 layering factors are usually not independently determined separately, but rather are optimal values of the lower layering factor based on mutual and organic relevance in order to form the lower layer with the desired properties. It is desirable to decide.

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

At least in the layer region of the upper layer in contact with the lower layer in the present invention, the layer contains carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), and germanium atoms while containing atoms for controlling conductivity (M). Neither atoms (Ge) nor tin atoms (Sn) are 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).

The atoms (M) for controlling conductivity contained in at least the layer region of the upper layer that is in contact with the lower layer may be uniformly distributed without unevenness in the layer region, or may be uniformly distributed in the layer region. However, there may be a portion that is contained in a state of being non-uniformly distributed in the layer thickness direction. However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary to be uniformly contained in the in-plane direction in order to make the characteristics in the in-plane direction uniform. .

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 throughout the layer region, or may be uniformly distributed in the layer region, but may be unevenly distributed in the layer thickness direction. There may be a portion contained in a distributed state.

However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary to be contained evenly and without unevenness from the viewpoint of achieving uniform characteristics in the in-plane direction.

Further, the upper layer in the present invention may contain a magnesium atom (Mg). When the magnesium atom (Mg) is contained in the upper layer, it may be contained in the entire layer region of the upper layer, or may be contained in a part of the upper layer, and in any case, Magnesium atom (Mg)
May be uniformly distributed in the layer region, or may be uniformly distributed in the layer region, but may be uniformly distributed in the layer thickness direction. There may be parts.

However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary to be contained evenly and without unevenness from the viewpoint of achieving uniform characteristics in the in-plane direction.

Further, a carbon atom (C) and / or a nitrogen atom (N)
And / or oxygen atom (O) (hereinafter "atom (CNO)")
(Hereinafter abbreviated as "layer region (CN
O) "and a layer region containing germanium atoms (Ge) and / or tin atoms (Sn) (hereinafter abbreviated as" atoms (GS) ") (hereinafter abbreviated as" layer region (GS) ") A layer region (hereinafter abbreviated as “layer region (Mg)”) containing magnesium atoms (Mg) (hereinafter abbreviated as “atom (Mg)”) is an atom (M) (hereinafter abbreviated) that controls conductivity. At least a layer region (hereinafter abbreviated as “layer region (M _B )”) in contact with at least the lower layer of the upper layer containing “atom (M)” Is also good.

Further, a layer region containing an atom (M) other than the layer region (M _B ) (hereinafter abbreviated as “layer region (Mr)”, and layer region (M _B )
And layer region (Mr) are collectively referred to as “layer region (M)”
, Layer area (CNO), layer area (GS), and layer area (Mg)
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. Typical example of the distribution of atoms (CNO) contained in the region (CNO) in the layer thickness direction, typical example of the distribution of atoms (GS) contained in the layer region (GS) in the layer thickness direction 3 shows a typical example of a distribution state of atoms (Mg) contained in (Mg) in a layer thickness direction. (Hereinafter, “layer region (Y)” represents layer region (M), layer region (CNO), layer region (GS), and layer region (Mg).
And an atom (M), an atom (CNO), an atom (GS), and an atom (Mg) are represented as “atom (Y)”. Therefore, the seventeenth
FIGS. 36 to 36 show the atoms (Y) contained in the layer region (Y).
Although a typical example of the distribution state in the layer thickness direction is shown, as described above, the layer region (M), the layer region (CNO), the layer region (GS), and the layer region (Mg) are substantially If they are the same layer region, the layer region (Y) is singularly included in the upper layer, and if they are not substantially the same layer region, the layer region (Y) is plurally included in the upper layer. ).

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 state such as taking a constant value that is the concentration C _211.

In the example shown in FIG. 22, the distribution concentration C of the atoms contained (Y) is, 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 Up to concentration C ₂₂₂
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 contained atoms (Y) gradually and continuously decreases from the concentration C ₂₃₁ until the position t _T from the position t _B , and at the position t _T forming a kind of distribution that the concentration C _232.

In the example shown in FIG. 24, the distribution concentration C of the atoms contained (Y) is, to the position t ₂₄₁ to the position t _B becomes a constant value consisting concentration C _241, up to the position t _T to the position t 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, to the position t ₂₆₁ to the position t _B becomes a constant value consisting concentration C _261, up to the position t _T to the position t ₂₆₁ reduced from the concentration C ₂₆₁ linear function to 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, to the position t ₂₈₁ to the position t _B becomes a constant value consisting concentration C _281, up to the position t _T to the position t ₂₈₁ reduced from the concentration C ₂₈₁ linear function to 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 atoms (Y) gradually increases continuously from the concentration C ₃₁₁ from the position t _B to the position t ₃₁₁ , and at the position t ₃₁₁ C ₃₁₂
From the position t ₃₁₁ to the position t _T, a distribution state is formed such that the density C ₃₁₃ takes a constant value.

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 next to a concentration C ₃₃₁ at position t ₃₃₁ gradually increases and from zero up to the position t ₃₃₁ to the position t _B ,
From the position t ₃₃₁ to the position t _T, a distribution state is formed such that the density C ₃₃₂ takes a constant value.

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), A1 (aluminum), Ga (gallium), In (indium), and T1 (thallium), with B, A1 and Ga being particularly preferred. Specific examples of Group V atoms include P (phosphorus), As (arsenic), and Sb.
(Antimony), Bi (bismuth) and the like, and P and As are particularly preferable. 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.
Incorporation of Group A or Group V or Group VI atoms, primarily to control conductivity type and / or conductivity and / or to inject charge between layer region (M _B ) and lower layer Or an effect of selectively controlling or improving the charge injection blocking property and / or the layer region (M)
The effect of improving the charge injection property between the upper layer and the layer region other than the layer region (M) can be obtained. Layer area (M)
The content of the atom (M) for controlling the conductivity contained in the metal is preferably 1 × 10 ^{−3 to} 5 × 10 ⁴ atomic ppm, more preferably 1 × 10 ⁻² to 1 × 10 ⁴ atomic ppm, Optimally 1 × 10 ^-1 ~
It is desirable that the concentration be 5 × 10 ³ atomic ppm. In particular, when the content of carbon atoms (C) and / or nitrogen atoms (N) and / or oxygen atoms (O) described below 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 carbon is preferably 1 × 10 ⁻³ to 1 × 10 ³ atomic ppm, and the carbon atom (C) and / or the nitrogen atom ( When the content of N) and / or oxygen atoms (O) exceeds 1 × 10 ³ atomic ppm, the content of atoms (M) for controlling conductivity is preferably 1 × 10 ^{−1 to} 5 × 10 ³ ppm. Desirably, it is ⁴ atomic ppm.

In the present invention, the carbon atom (C) is added to the layer region (CNO).
And / or containing 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 region (CNO) and Layer area of layer (CNO)
The effect of improving the adhesion between the other layer regions 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.
It is desirable to set the atomic ppm, more preferably 1 × 10 ^{1 to} 5 × 10 ⁵ atomic ppm, 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 to} 9 × 10 ⁵ atomic ppm.
It is desirable that the concentration be from × 10 ^{2 to} 5 × 10 ⁵ atomic ppm.

In the present invention, the germanium atom (Ge) and / or the tin atom (Sn) are contained in the layer region (GS) to mainly control the spectral sensitivity. When long-wavelength light is used, an effect of improving long-wavelength light sensitivity can be obtained. Germanium atoms (Ge) contained in the layer region (GS)
And / or the content of tin atoms (Sn) is preferably 1 to 9.5 × 10 ⁵ atomic ppm, more preferably 1 × 10 ² to 8 ppm.
It is desirable that the concentration be set to × 10 ⁵ atomic ppm, optimally 5 × 10 ^{2 to} 7 × 10 ⁵ atomic ppm.

In the present invention, the hydrogen atoms (H) and / or the halogen atoms (X) contained in the upper layer can compensate for the dangling bonds of the silicon atoms (Si) to 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
It is desirable that the concentration be 4 × 10 ⁵ 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 ×
When the concentration is 10 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 from × 10 ³ to 4 × 10 ⁵ atomic ppm. Further, when the upper layer is made of poly-Si (H, X),
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 2 × 10 ⁵ atomic ppm. Is desirable, and A
-Si (H, X) is preferably 1 × 10 ⁴ to
Preferably, it is 7 × 10 ⁵ atomic ppm.

In the present invention, the content of magnesium atoms (Mg) contained in the upper layer is preferably 1 × 10 ⁻³ to
The concentration is preferably 1 × 10 ⁴ atomic ppm, more preferably 1 × 10 ^-2 to 1 × 10 ³ atomic ppm, and most preferably 5 × 10 ^{-2 to} 5 × 10 ² atomic ppm.

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 in particular, the glow discharge method, the sputtering method, and the ion plating method. Method, HRCVD method and FOCVD method are suitable. These methods may be used together in the same apparatus system.

For example, in order to form an upper layer made of Non-Si (H, X) by a glow discharge method, basically, a gas for supplying Si capable of supplying 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) Deposition in which a Ge supply gas capable of supplying atoms (Ge) and / or a Sn supply gas capable of supplying tin atoms (Sn) and a Mg supply gas capable of supplying magnesium atoms (Mg) can be reduced in pressure. The gas is introduced into the room at a desired gas pressure, and Cause glow discharge to the product chamber, Non-S in advance on a support surface forming a predetermined advance the lower layer are installed in a predetermined position
What is necessary is just to form the layer which consists of i (H, X).

In order to form an upper layer composed of Non-Si (H, X) by HRCVD, a Si supply gas capable of supplying silicon atoms (Si) and a halogen atom (X) are basically supplied. X supply gas to be obtained, and M supply gas to supply atoms (M) for controlling conductivity and / or C supply gas and / or nitrogen atoms to supply carbon atoms (C) if necessary. N) supply gas capable of supplying N) and / or O supply gas capable of supplying oxygen atoms (O) and / or Ge supply gas capable of supplying germanium atoms (Ge) and / or tin atoms (Sn) Sn supply gas that can supply
Mg supply gas that can supply magnesium atoms (Mg)
As required, separately or together, a glow discharge is generated in the activation space by 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 reduced in pressure, or An active species (A) is generated by heating or the like, and an H supply gas capable of supplying hydrogen atoms (H) is similarly introduced into another activation space to generate an active species (B). The seed (A) and the active species (B) are separately introduced into the deposition chamber, and Non-Si is 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 (H, X).

In order to form an upper layer composed of Non-Si (H, X) by the FOCVD method, basically, an Si supply gas capable of supplying silicon atoms (Si) and a hydrogen atom (H) are supplied. H to get
Supply gas, and M supply gas and / or C supply gas and / or nitrogen atom (N) capable of supplying atoms (M) and / or carbon atoms (C), as necessary, for controlling conductivity. Supply gas for supplying N and / or O supply gas for supplying oxygen atoms (O) and / or Ge supply gas and / or tin atoms (Sn) for supplying germanium atoms (Ge) Possible Sn supply gas,
Mg supply gas that can supply magnesium atoms (Mg)
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 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), magnesium atom (Mg) (hereinafter collectively abbreviated as “atom (Z)”) by changing the distribution concentration C in the layer thickness direction to obtain a desired layer thickness direction. In order to form a layer having a distribution profile (depth profile), in the case of the glow discharge method, the HRCVD method, and the FOCVD method, a gas for supplying an atom (Z) whose distribution concentration is to be changed is set to a desired gas flow rate. This is achieved by appropriately changing the temperature according to the rate-of-change curve and introducing it 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.

As another method, the flow rate setting of the mass flow controller that controls the gas flow rate is appropriately changed by any method generally used such as manually or using a programmable control device.

Examples of the substance that can be a 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 terms of ease of handling at the time of forming a layer and high Si supply efficiency. Further, these Si supply gases 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, halogens in gaseous state or gasizable halogens such as halogen gas, halides, interhalogen compounds, and halogen-substituted silane derivatives. Compounds.

Further, in the present invention, a silicon hydride compound containing a halogen atom (X), which is a gas state or can be gasified and has a silicon atom (Si) and a halogen atom (X) as constituents, is also effectively used in the present invention. Can be mentioned.

Specifically, fluorine is a halogen compound that can be preferably used in the present invention, chlorine, bromine, halogen gas _{iodine, 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 (X), that is, a silane derivative substituted with a so-called halogen atom (X), specifically, a silicon halide such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiBr ₄ is preferable. Can be listed as

When a silicon compound containing a halogen atom (X) is used to form a characteristic electrophotographic light receiving member of the present invention by a glow discharge method or an HRCVD method, hydrogenation as a gas for supplying Si is performed. An upper layer made of Non-Si (H, X) containing a halogen atom (X) can be formed on a desired lower layer without using silicon gas.

According to glow discharge method and HRCVD method, halogen atom (X)
When forming an upper layer containing
By using silicon halide as a supply gas, an upper layer can be formed on a desired support. However, in order to make the introduction ratio of hydrogen atoms (H) easier, Such a gas may be mixed with a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms (H) to form a layer.

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 halogen compound described above as the halogen atom supply gas or the halogen atom (X)
Are used as effective ones. In addition, hydrogen halides such as HF, HCl, HBr, HI, SiH ₃ F, SiH ₂ F ₂ , SiHF ₃ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHC
Halogen-substituted silicon hydrides such as l ₃ , SiH ₂ Br ₂ , SiHBr _{3 and the} like, and substances in a gas state or capable of being gasified can also be cited as effective raw materials for forming the upper layer. Among these substances, a halide containing a hydrogen atom (H) is a hydrogen atom which is extremely effective for controlling electric or photoelectric characteristics simultaneously with the introduction of the halogen atom (X) into the upper layer. Since (H) is also introduced, it is used as a suitable halogen supply gas in the present invention.

To structurally introduce hydrogen atoms (H) into the upper layer,
In addition to the above, discharge is caused by coexistence of H ₂ or silicon hydride such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ and the above-mentioned Si supply gas in the deposition chamber. But you can do it.

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 structurally introduce a Group III atom, a Group V atom, or a Group VI atom, a source material for supplying a Group III atom, a source material for supplying a Group V atom, or The source material for supplying group VI atoms may be supplied in a gaseous state into the deposition chamber together with other source materials for forming the upper layer. The raw material for supplying Group III atoms, the raw material for supplying Group V atoms, or the raw material for supplying Group VI atoms may be gaseous at room temperature and normal pressure, or at least under conditions of layer formation. It is desirable to employ a material which can be easily gasified. III
As a raw material for supplying group atoms, specifically, for supplying boron atoms, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B
₆ H _12, B ₆ H ₁₄ borohydride such as, BF _3, BCl _3, BBr boron halides such as _3. In addition, AlCl ₃ , GaCl ₃ , Ca
(CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like can also be mentioned.

As a raw material for supplying group V atoms, the present invention effectively uses PH ₃ , P for supplying phosphorus atoms.
₂ H _4, etc. of hydrogen phosphorus _{halides, PH 4 I, PF 3,} PF 5, PCl 3, PCl 5, PB
phosphorus halides such as r ₃ , PBr ₅ and PI ₃ ; In _{addition, AsH 3, AsF 3, AsCl} 3, AsBr 3, AsF 5, SbH 3, SbF 3, Sb
F ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned as effective raw materials for supplying group V atoms.

As a raw material for supplying Group VI atoms, 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,
Substances in a gaseous state or capable of being gasified, such as C ₄ H ₄ S, (CH ₃ ) ₂ S, and (C ₂ H ₅ ) ₂ S, are mentioned. In addition, SeH ₂ , SeF ₆ , (CH ₃ ) ₂
Substances in a gaseous state or capable of being gasified, such as Se, (C ₂ H ₅ ) ₂ Se, TeH ₂ , TeF ₆ , (CH ₃ ) ₂ Te, and (C ₂ H ₅ ) ₂ Te.

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

Carbon atoms (C) or nitrogen atoms (N) in the upper layer
Alternatively, to structurally introduce oxygen atoms (O), a raw material for supplying carbon atoms (C), a raw material for supplying nitrogen atoms (N), or an oxygen atom (O)
The raw material for supply may be supplied in a gaseous state into the deposition chamber together with other raw materials for forming the upper layer.
The raw material for supplying carbon atoms (C), the raw material for supplying nitrogen atoms (N), or the raw material for supplying 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 supplying carbon atoms (C) include C and H as constituent atoms, for example, a saturated hydrocarbon having 1 to 4 carbon atoms, 2 to 2 carbon atoms.
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 ₂ 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 ).

In addition, CF ₄ , CCl ₄ , and CH ₃ can be supplied in addition to supplying carbon atoms (C), because halogen atoms (X) can be supplied.
Halocarbon gases CF ₃ and the like.

Starting materials that can be effectively used as a source gas for supplying nitrogen atoms (N) include 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 ₃ N) can be supplied in addition to supplying nitrogen atoms (N) because halogen atoms (X) can be supplied.
₄ N ₂ ) and the like.

Starting materials that can be effectively used as source gas for supplying 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 ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atom ( For example, lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ) containing Si), an oxygen atom (O) and a hydrogen atom (H) as constituent atoms may be mentioned. it can.

In order to structurally introduce germanium (Ge) or tin atoms (Sn) into the upper layer, a raw material for supplying germanium (Ge) or tin atoms (Sn) should be used during layer formation.
The raw material for supply may be supplied in a gaseous state into the deposition chamber together with other raw materials for forming the upper layer.
As a raw material for supplying germanium (Ge) or a raw material for supplying tin atom (Sn), a gaseous material at normal temperature and normal pressure or a material that can be easily gasified at least under layer forming conditions is adopted. It is desirable to be done.

GeH ₄ , Ge
_{2 H 6, Ge 3 H 8} , Ge 4 H gaseous state, such as ₁₀ or the like as germanium hydride can be gasified is effectively used, in particular the layer created when working easy handling, Ge supply efficiency GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferable in terms of, for example, the quality of the film.

In addition, GeHF ₃ , GeH ₂ F ₂ , Ge 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 , Ge
Germanium hydride halides such as H ₃ I GeF ₄ , GeCl ₄ , Ge
Substances in a gaseous state such as Br ₄ , GeI ₄ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI _{2, and} other germanium halides, or substances that can be gasified can also be mentioned as effective raw materials for forming the upper layer.

Substances that can be Sn supply gas include SnH ₄ , Sn
It listed _{as 2 H 6, Sn 3 H 8} , Sn 4 tin hydride which may or gasified gas conditions such as H ₁₀ is effectively used,
In particular, SnH ₄ , Sn ₂ H ₆ , and Sn ₃ H ₈ are preferable in terms of ease of handling during layer formation work, high Sn supply efficiency, and the like.

In addition, SnHF ₃ , SnH ₂ F ₂ , SnH ₃ F ,, nHCl ₃ , SnH ₂ Cl ₂ ,
SnH ₃ Cl, SnHBr ₃ , SnH ₂ Br ₂ , SnH ₃ Br, SnHI ₃ , SnH ₂ I ₂ , Sn
Tin halides such as H ₃ I, SnF ₄ , SnCl ₄ , SnBr ₄ , S
Substances in the gaseous state or gasifiable substances such as tin halides such as nI ₄ , SnF ₂ , SnCl ₂ , SnBr ₂ , SnI _{2 and the} like can also be mentioned as effective starting material for forming the upper layer.

In order to structurally introduce magnesium atoms (Mg) into the upper layer, it is necessary to form a raw material for supplying magnesium atoms (Mg) in a gaseous state in the deposition chamber during the layer formation to form the upper layer. What is necessary is just to introduce with other raw material. As a material that can be used as a raw material for supplying magnesium atoms (Mg), it is preferable to employ a material that is gaseous at normal temperature and normal pressure or that can be easily gasified at least under conditions for forming a layer.

Substances that can be used as the Mg supply gas include organic metals containing magnesium atoms (Mg), which can be used effectively. In particular, they are easy to handle during layer formation work and have high Mg supply efficiency. And bis (cyclopentadienyl) magnesium (II) complex salt (Mg (C ₅ H ₅ ) ₂ ).

In addition, these Mg supply gases may be replaced with H ₂ , He,
It may be diluted with a gas such as r or Ne before use.

In the present invention, the thickness of the upper layer is from 1 to 130 from the viewpoint of obtaining desired electrophotographic properties and economical effects.
μm, 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

When the upper layer is constituted by selecting A-Si (H, X) as Non-Si (H, X), the optimum range of the support temperature (Ts) is appropriately selected according to the layer design. Usually 50 ~
It is desirable that the temperature be 400 ° C, preferably 100 to 300 ° C. When the upper layer is formed by selecting non-Si (H, X) and poly-Si (H, X), there are various methods for forming the layer. For example, the following method is used. No.

One method is to raise the substrate temperature to a high temperature,
In this method, the temperature is set to 0 to 600 ° C., and a 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 a glow discharge method, the optimum range of discharge power supplied into the deposition chamber is appropriately selected according to 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 , and 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 layering factors are usually not independently determined separately, but rather are optimized based on mutual and organic relationships to form an upper layer with desired properties. 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.

In the figure, 1071, 1072, 1073, 1074, 1075, 1076, 1077, 1079 gas cylinders, 1078 sealed containers and 1080 sealed containers are sealed with a source gas for forming each layer of the present invention. 1071 is a cylinder of SiH ₄ gas (99.99% purity), 1
072 is a H ₂ gas (purity 99.9999%) cylinder, 1073 is a CH ₄ gas (purity 99.999%) cylinder, 1074 is a PH diluted with H ₂ gas.
₃ gas (purity 99.999%, hereinafter abbreviated as “PH ₃ / H ₂ ”) cylinder, 1075 is B ₂ H ₆ gas (purity 99.999%) diluted with H ₂ gas
%, Hereinafter abbreviated as “B ₂ H ₆ / H ₂ ”), 1076 is a cylinder of NO gas (purity 99.9999%), and 1077 and 1079 are He gas (purity 99.999%).
%) Cylinder, 1078 is a sealed container filled with AlCl ₃ (purity 99.99%), and 1080 is a sealed container filled with Mg (C ₅ H ₅ ) ₂ (purity 99.99%).

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, gas cylinders 1071 to 1077 and valves 1079 to 1079
1058, the inflow valves 1031 to 1038, and the leak valve 1015 of the deposition chamber 1001 are confirmed to be closed, and the outflow valves 1041 to 1048 and the auxiliary valve 1018 are confirmed to be open. Was opened, and the inside of the deposition chamber 1001 and the gas piping were evacuated by a vacuum pump (not shown).

Next, when the reading of the vacuum gauge 1017 became about 1 × 10 ⁻³ Torr, the auxiliary valve 1018 and the outflow valves 1041 to 1048 were closed.

Thereafter, SiH ₄ gas and gas cylinder 10
H ₂ gas from 72, CH ₄ gas from gas cylinder 1073, PH ₃ / H ₂ gas from gas cylinder 1074, B ₂ H ₆ / H ₂ from gas cylinder 1075
Gas, NO gas from gas cylinder 1076, gas cylinder 1077,107
From No. 9, He gas was introduced by opening valves 1051 to 1058, and each gas pressure was adjusted to ² kg / cm ² by pressure regulators 1061 to 1068.

Next, the inflow valves 1031 to 1038 were gradually opened, and the above gases were introduced into the mass flow controllers 1021 to 1028. 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.
8, AlCl ₃ gas diluted with He gas (hereinafter abbreviated as “AlCl ₃ / He”) is introduced, and He gas from gas cylinder 1079 is supplied to mass flow controller 1028.
Since it comes through a sealed container 1080 filled with Mg (C ₅ H ₅ ) ₂ , H
eMg (C ₅ H ₅ ) ₂ gas diluted with gas (hereinafter “Mg (C ₅ H ₅ ) ₂ / H
e ").

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, 1047, 1
048 and gradually open the SiH ₄ gas auxiliary valve 1018, H ₂
Gas, AlCl ₃ / He gas, Mg (C ₅ H ₅ ) ₂ / He gas into gas inlet tube 10
The gas was introduced into the deposition chamber 1001 through the gas discharge hole 1009 of 08. At this time, the flow rate of SiH ₄ gas is 50 SCCM and the flow rate of H ₂ gas is 10 SCC
M, AlCl ₃ / He gas flow rate is 120 SCCM, Mg (C ₅ H ₅ ) ₂ / He gas flow rate is 5 SCCM so that each mass flow controller 1
Adjusted at 021,1022,1027,1028. 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. Then, set the power of the RF power source (not shown) to 5 mW / cm ^3, the high-frequency matching box 1
RF power was introduced into the deposition chamber 1001 through 012 to generate RF glow discharge, and the formation of the lower layer on the cylindrical aluminum-based support was started. During the formation of the lower layer, the SiH ₄ gas flow rate
As a constant flow of 50 SCCM, as H ₂ gas flow rate increases at a constant rate 200SCCM from 10 SCCM, as AlCl ₃ / the He gas flow rate decreases at a constant rate 40SCCM from 120 SCCM, Mg (C ₅ H _{5) 2} / He gas flow rate mass flow controller so that a constant flow rate of 5 SCCM 1021,1022,1027,1028
Was adjusted and the lower layer with a thickness of 0.05 μm was formed.
Glow discharge is stopped, and outflow valves 1041, 1042, 1047, 1
The gas flow into the deposition chamber 1001 was stopped by closing the 048 and the auxiliary valve 1018, and the formation of the lower layer was completed.

Next, in order to form the first layer region of the upper layer, the outflow valves 1041, 1042, 1045 and the auxiliary valve 1018 are gradually opened, and SiH ₄ gas, H ₂ gas, and B ₂ H ₆ / H ₂ gas are supplied. The gas was 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 100 SCCM, the flow rate of H ₂ gas is 500 SCCM,
The mass flow controllers 1021, 1022, and 1025 adjusted the B ₂ H ₆ / H ₂ gas flow rate to be 200 ppm with respect to the SiH ₄ gas flow rate. 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. Then, the deposition chamber 1001 through the high-frequency matching box 1012 to set the power of the RF power source (not shown) to 8 mW / cm ³
RF power is introduced to generate an RF glow discharge, start forming a first layer region of the upper layer on the lower layer, and form an RF glow discharge when the first layer region of the upper layer having a thickness of 3 μm is formed. To stop the flow of gas into the deposition chamber 1001 by closing the outflow valves 1041, 1042, 1045 and the auxiliary valve 1018,
The formation of the first layer region of the upper layer has been 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. Thereafter, to rise to the introduced RF glow discharge RF power to the deposition chamber 1001 through the high-frequency matching box 1012 to set the power of the RF power source (not shown) to 15 mW / cm ^3, first the first layer region of the upper layer When the formation of the second layer region was started and the second layer region of the upper layer having a thickness of 20 μm was formed, the RF glow discharge was stopped, and the outflow valves 1041 and 1042 and the auxiliary valve 1018 were closed, and the deposition chamber 1 was closed.
The flow of gas into 001 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 mass flow controllers 1021 and 1023 adjusted the flow rates of the SiH ₄ gas to 50 SCCM and the flow rate of the CH ₄ gas to 500 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 0.4 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, or,
Close the outflow valve 1041, 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 in the deposition chamber 1001, outflow valves 1041 to 1048
It is necessary to close the outflow valves 1041 to 1048, open the auxiliary valve 1018, open the main valve fully, and once evacuate the system to a high vacuum in order to avoid remaining in the piping from to the deposition chamber 1001 Perform according to.

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.

In forming the <Comparative Example> lower layer, other than not using H _{2 gas, Mg (C 5 H 5)} 2 / He gas was prepared an electrophotographic light-receiving member in the same preparation conditions as in Example 1 . 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 respectively set in an electrophotographic apparatus in which a copying machine NP-7550 made by Canon was remodeled for experiments, and several conditions were set under various conditions. The electrophotographic properties were checked.

These light receiving members for electrophotography were found to have a characteristic of exhibiting extremely good charging ability. However, when the number of spots was compared as an image characteristic, it was found that the number of spots having a diameter of 0.1 mm or less was particularly large. It was found that the light receiving member for electrophotography had a number of spots of 1/3 or less of the light receiving member for electrophotography of Comparative Example. Further, in order to compare the degree of roughness, 100 points of image density were measured using a circular area having a diameter of 0.05 mm as one unit, and the variation of the image density was evaluated. The member had a variation of 1/4 or less of the electrophotographic light receiving member of the comparative example, and the electrophotographic light receiving member of Example 1 was visually superior to the electrophotographic light receiving member of the comparative example. I understood.

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 1/4 or less of that of the electrophotographic light receiving member of the comparative example.

The lower layer of the electrophotographic light-receiving member of Example 1 was replaced with SIMS.
As a result, it was found that the contents of silicon atoms, hydrogen atoms and aluminum atoms in the thickness direction changed as desired.

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, NO gas and B ₂ H ₆ / H ₂ gas were further used, the manner of changing the AlCl ₃ / He gas flow rate was changed, and the production conditions shown in Table 3 were used. 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.

Without using the CH ₄ gas in the upper layer of the <Example 3> Example 1, 4
Under the conditions shown in the table, a light-receiving member for electrophotography was prepared in the same manner as in Example 1, and the same evaluation was carried out. Effect was obtained.

<Example 4> In Example 1, N ₂ gas (purity 9) was supplied from a cylinder (not shown).
9.9999%), He gas (purity 99.9999%), and SiF ₄ gas were further used, and a light receiving member for electrophotography was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 5, and the same evaluation was performed. As a result, as in the case of Example 1, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

Example 5 In the lower layer of Example 1, Al (CH ₃ ) was used instead of AlCl _3.
3 (99.99% purity), further use CH ₄ gas,
Ar gas (purity 99.9999) was applied to the SiF ₄ gas cylinder in the upper layer.
%) Cylinders and NO gas cylinders with NH ₃ gas (purity 99.99%
9%) Instead of a cylinder, according to the preparation conditions shown in Table 6,
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 6 The lower layer further uses SiF ₄ gas from a cylinder (not shown), and the upper layer further uses PH ₃ / H ₂ gas.
Under the conditions shown in Table 7, 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 7> In the lower layer of Example 1, PF ₅ gas diluted with He gas (purity: 99.999%, abbreviated as “PF ₅ / He”) and NO gas were used, and PF ₅ / He and SiF ₄ gases were 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 8, and the same evaluation was performed. A good effect was obtained, which was improved against roughening and layer peeling.

<Example 8> Using the unillustrated cylinders from H ₂ S gas in the lower layer in Example 1 (purity _{99.9%), PH 3 / H} 2 gas in the upper layer, the N ₂ gas from a cylinder (not shown) further Under the conditions shown in Table 9, a light-receiving member for electrophotography was prepared in the same manner as in Example 1, and the same evaluation was carried out. A good effect was obtained which was improved.

<Example 9> In Example 1, the CH ₄ gas cylinder was replaced with a C ₂ H ₂ gas (99.
Changed 9999%) gas cylinder, by changing the PH ₃ / H ₂ gas cylinder in GeF ₄ gas cylinder, the generating conditions shown in Table 10, to create the electrophotographic light-receiving member as in Example 1, the same evaluation 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 10> A B ₂ H ₆ gas cylinder was diluted with He gas into BF ₃ gas (purity 9).
9.999%, hereinafter abbreviated as “BF ₃ / He”), and a light-receiving member for electrophotography was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 11, 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 11> In Example 1, the NO gas cylinder was changed to an NH ₃ gas cylinder, and a SiF ₄ gas was further used from a cylinder (not shown).
Under the 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, spots, roughening, and layer peeling were improved. Good effects were obtained.

<Example 12> In the upper layer of Example 6, a SiF ₄ 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 6 under the preparation conditions shown in Table 13. When a similar evaluation was performed, the same as in Example 6,
A good effect of improving the peeling of the layer was obtained.

<Example 13> PH ₃ / H ₂ gas, Si ₂ F ₆ gas (purity 9
9.99%) and Si ₂ H ₆ gas (purity 99.99%)
Under the preparation conditions shown in Table 14, an electrophotographic light-receiving member was prepared in the same manner as in Example 9, and the same evaluation was performed.
As in the case of Example 9, a good effect of improving spotting, roughening, and layer peeling was obtained.

Example 14 In the lower layer, SiF ₄ gas was changed to Si ₂ F ₆ gas and B ₂ H ₆ / H
Further using ₂ gas, further using PH ₃ / H ₂ gas in the upper layer, the generating conditions shown in Table 15, to create the electrophotographic light-receiving member as in Example 11, the same evaluation As a result, similar effects to those of Example 11 were obtained, and a favorable effect of improving spotting, roughening, and layer peeling was obtained.

Example 15 PH ₃ / H ₂ gas in the upper layer, GeH from a cylinder (not shown)
₄ Further use of gas, and under the preparation conditions shown in Table 16,
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 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 performed except that an electrophotographic apparatus was used which was modified from the copying machine NP-9030 for experiments, and the same results as in Example 1 were obtained. 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 conducted except that an electrophotographic apparatus modified from the copying machine NP-150Z was used for the experiment. 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 modified from the copying machine FC-5 for experiment was used. As a result, the same improvement as in Example 1 was obtained for spotting, roughening, and layer peeling. Good effects were 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, the cylindrical aluminum-based support subjected to mirror finishing was further turned 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 1028. However, a SiF ₄ gas cylinder was used instead of the PH ₃ / H ₂ gas cylinder.

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
1,1042,1044～1048 and opening the auxiliary valve 1018 gradually, SiH ₄ gas, H ₂ gas, SiF ₄ gas, B ₂ H ₆ / H ₂ gas, NO gas, AlCl ₃ / He gas, Mg (C ₅ H ₅ ) ₂ / He gas gas inlet tube 1110
(Not shown) into the plasma generation region 1109. At this time, the SiH ₄ gas flow rate was 150 SCCM, the H ₂ gas flow rate was 20 SCCM, the SiF ₄ gas flow rate was 10 SCCM, the B ₂ H ₆ / H ₂ gas flow rate was 50 ppm with respect to the SiH ₄ gas flow rate, and the NO gas flow rate was 5 SCCM.
AlCl ₃ / He gas flow rate is 400 SCCM, Mg (C ₅ H ₅ ) ₂ / He gas flow rate is 1
Each mass flow controller 102 to be 0SCCM
Adjusted at 1,1022,1024-1028. 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, so that SiH ₄ gas flow rate is constant flow rate of 150 SCCM, as H ₂ gas flow rate increases at a constant rate 500SCCM from 20 SCCM, SiF ₄ gas flow rate so that a constant flow rate of 10SCCM In addition, the B ₂ H ₆ / H ₂ gas flow rate withstands the SiH ₄ gas flow rate.
The NO gas flow rate is 5 SCCM so that it becomes 50 ppm, and the AlCl ₃ / He gas flow rate is 80 SCCM at the upper layer side 0.01 μm so that the gas flow rate decreases from 400 SCCM at the support side 0.01 μm to 80 SCCM at a constant rate.
Mg (C ₅ H ₅ ) ₂ / He to decrease at a constant rate from 50 SCCM
Adjust the mass flow controllers 1021, 1022, 1024 to 1028 so that the gas flow rate is a constant flow rate of 10 SCCM, and
When the lower layer of μm is formed, the μW glow discharge is stopped, and the outflow valves 1041, 1042, 1044 to 1048 and the auxiliary valve 1018 are closed to stop the flow of gas into the plasma generation region 1109, and the lower layer is formed. Finished.

Next, in order to form the first layer region of the upper layer, the outflow valves 1041, 1042, and 1045 and the auxiliary valve 1018 are gradually opened, and SiH ₄ gas, H ₂ gas, and B ₂ H ₆ / H ₂ gas are supplied. The gas was introduced into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, the mass flow controllers 1021, 1022, and 1025 adjusted the SiH ₄ gas flow rate to 700 SCCM, the H ₂ gas flow rate to 500 SCCM, and the B ₂ H ₆ / H ₂ gas flow rate to 200 ppm with respect to the SiH ₄ gas flow rate. did. 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. Start forming, 3μ layer thickness
The first layer region of the upper layer was formed.

Next, to form the second layer region of the upper layer, the outflow valves 1041, 1042, 1044 and the auxiliary valve 1018 are gradually opened,
SiH ₄ gas, H ₂ gas, and SiF ₄ 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, the SiH ₄ gas flow rate was 700 SCCM, and the H ₂ gas flow rate was 50
The mass flow controllers 1021, 1022, 1024 adjusted the flow rates of 0 SCCM and SiF ₄ gas to 30 SCCM. The pressure in the deposition chamber 1101 was adjusted to be 0.5 mTorr. After that, the power of a μW power supply (not shown) was set to 0.5 W / cm ³ , 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. The formation of the second layer region was started, and the second layer region of the upper layer having a layer thickness of 20 μm was formed.

Next, in order to form the third layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened so that the SiH ₄
Gas and CH ₄ gas were introduced into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. This time
The mass flow controllers 1021 and 1023 adjusted the flow rates of SiH ₄ gas to 150 SCCM and 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) is set to 0.5 W / cm ³ to generate a μW glow discharge in the plasma generation region 1109, and a 1 μm thick upper layer having a thickness of 1 μm is formed on the second upper layer region. 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> An electrophotographic light-receiving member was prepared in the same manner as in Example 9 under the preparation conditions shown in Table 23, and the same evaluation was performed.
As in the case of Example 9, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 25> An electrophotographic light-receiving member was prepared in the same manner as in Example 10 under the preparation conditions shown in Table 24, and the same evaluation was performed.
As in the case of Example 10, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 26> Under the conditions shown in Table 25, a light receiving member for electrophotography was prepared in the same manner as in Example 11, and the same evaluation was performed. As in Example 11, a spot, a rough layer, and a layer peeled off. A good effect was obtained which was improved with respect to.

<Example 27> Under the conditions shown in Table 26, a light-receiving member for electrophotography was prepared in the same manner as in Example 12, and the same evaluation was carried out. As in Example 12, spots, roughening, and layer peeling were observed. A good effect was obtained which was improved with respect to.

<Example 28> Under the conditions shown in Table 27, a light-receiving member for electrophotography was prepared in the same manner as in Example 13, and the same evaluation was carried out. As in Example 13, spots, roughening, and layer peeling were observed. A good effect was obtained which was improved with respect to.

<Example 29> Under the conditions shown in Table 28, an electrophotographic light-receiving member was prepared in the same manner as in Example 14, and the same evaluation was performed. As in Example 14, the spots, roughening, and layer peeling were observed. A good effect was obtained which was improved with respect to.

<Example 30> Under the conditions shown in Table 29, a light-receiving member for electrophotography was prepared in the same manner as in Example 4, and the same evaluation was carried out. As in Example 4, spots, roughening, and layer peeling were observed. A good effect was obtained which was improved with respect to.

<Example 31> Under the conditions shown in Table 30, a light-receiving member for electrophotography was prepared in the same manner as in Example 6, and the same evaluation was carried out. As in Example 6, spots, roughening, and layer peeling were observed. A good effect was obtained which was improved with respect to.

<Example 32> Under the conditions shown in Table 31, a light receiving member for electrophotography was prepared in the same manner as in Example 12, and the same evaluation was performed. As in Example 12, a spot, a roughening, and a layer peeling were observed. A good effect was obtained which was improved with respect to.

<Example 33> Under the conditions shown in Table 32, an electrophotographic light-receiving member was prepared in the same manner as in Example 31, and the same evaluation was carried out. As in Example 31, spots, roughening, and layer peeling were observed. A good effect was obtained which was improved with respect to.

Example 34 The lower layer of the electrophotographic light-receiving member of the present invention was formed by RF sputtering, and the upper layer was formed by RF glow discharge decomposition.

FIG. 42 includes a source gas supply device 1500 and a deposition device 1501. 1 shows an apparatus for manufacturing a light receiving member for electrophotography by an RF sputtering method.

In the figure, 1405 is Si, Al, which is a raw material for forming the lower layer.
The target is made of Mg, and the mixing ratio in the thickness direction is changed so that each atom has a desired distribution state.

The gas cylinders 1408, 1409, 1410 in the figure are sealed with a source gas for forming a lower layer, 1408 is a cylinder of SiH ₄ gas (purity 99.99%), and 1409 is a H ₂ gas (purity 99.9999).
%) Cylinder 1410 is an Ar gas (purity 99.999%) cylinder.

In the figure, reference numeral 1402 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 1401 and the gas pipe were evacuated until the pressure in the deposition chamber 1401 became 1 × 10 ⁻⁶ Torr.

Thereafter, each gas was introduced into the mass flow controllers 1412 to 1414 in the same manner as in Example 1.

Further, the temperature of the cylindrical aluminum-based support body 1402 installed in the deposition chamber 1401 is controlled by a heater (not shown).
Heated to ° C.

After the preparation for film formation was completed as described above, the lower layer was formed on the cylindrical aluminum-based support 1402.

To form the lower layer, SiH ₄ gas by opening gradually the outflow valves 1420,1421,1422 and auxiliary valve 1432, H ₂ gas,
Ar gas is caused to flow into the deposition chamber 1401. At this time, the SiH ₄ gas flow rate was 20 SCCM, the H ₂ gas flow rate was 5 SCCM, and the Ar gas flow rate was 100 SCCM.
Each mass flow controller 1412,1 to become CM
Adjusted at 413,1414. The pressure in the deposition chamber 1401 is 0.01 Torr
The opening of the main valve 1407 was adjusted while looking at the vacuum gauge 1435 so that. Then, the power of the RF power supply (not shown) was increased by 1 mW /
RF power was introduced between the target 1405 and the aluminum-based support 1402 through a high-frequency matching box 1433 set to cm ³ to generate an RF glow discharge, and the formation of a lower layer on the cylindrical aluminum-based support was started. During the formation of the lower layer, the flow rate of the SiH ₄ gas was set to be a constant flow rate of 20 SCCM.
Adjust the mass flow controllers 1412, 1413, 1414 so that the H ₂ gas flow rate increases from 5 SCCM to 100 SCCM at a constant rate, and the Ar gas flow rate becomes a constant flow rate of 100 SCCM.
When the lower layer of 0.02 μm was formed, the RF glow discharge was stopped, and the outflow valves 1420, 1421, 1423 and the auxiliary valve
1432 was closed, the flow of gas into the deposition chamber 1401 was stopped, and the formation of the lower layer was completed.

During the formation of the lower layer, the cylindrical aluminum-based support 1402 is rotated at a desired speed by a driving device (not shown) in order to make the layer formation uniform.

Next, to form the upper layer, an electrophotographic light-receiving member was prepared in the same manner as in Example 10 using the apparatus shown in FIG. As a result, as in Example 10, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

[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. Especially excellent electrical, optical,
It shows photoconductive properties, image properties, durability, and usage 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, a halftone is clearly produced, and a high-quality image with high resolution can be stably and repeatedly obtained.

Furthermore, image defects are generated due to relatively short-time mechanical pressure applied to the light receiving member for electrophotography, and Non-S
Prevents peeling of the i (H, X) 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, as a distinctive feature of the lower layer containing magnesium atoms (Mg), the injection and adhesion of electric charge (photocarrier) between the aluminum-based support and the upper layer and the lower layer. Since the traveling property of the electric charge (photocarrier) in the layer is remarkably improved, there is a feature that a remarkable improvement in image characteristics and durability is observed.

Further, in the present invention, by injecting atoms (M) for controlling conductivity into a layer region in contact with the lower layer in the upper layer, charge injection or charge injection between the upper layer and the lower layer is prevented. Can be selectively controlled or improved, image characteristics such as roughness and spots are improved, halftones are clearly output, and high resolution, high quality images can be repeatedly obtained stably. Charging ability, sensitivity and durability are also 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 aluminum atoms (Al), magnesium atoms (Mg), germanium atoms (Ge) and tin atoms (Sn) and halogen atoms (X) contained in the lower layer, respectively. FIG. 9 is an explanatory view of distribution states of atoms for controlling durability (CNO _c ) and atoms for adjusting image quality (Mc). FIGS. 9 to 16 show silicon atoms (Si) contained in the lower layer, Hydrogen atom (H), magnesium atom (Mg), germanium atom (Ge) optionally contained
FIG. 17 is an explanatory view of distribution states of tin atoms (Sn), halogen atoms (X), atoms controlling durability (CNO _c ), and atoms adjusting image quality (Mc). Atoms (M), carbon atoms (C) and / or nitrogen atoms (N) and / or oxygen atoms (O), germanium atoms (Ge) and / or tin atoms (Sn) contained in the layer FIG. 37 is an explanatory view of a distribution state of magnesium atoms (Mg). 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. FIG. 38 is an enlarged view of a cross section of an aluminum-based support when the light-receiving member for electrophotography of the present invention is formed in a V-shaped cross section, and FIG. 39 is a view showing the present invention. Aluminum for forming electrophotographic light-receiving members FIG. 40 is an enlarged view of the cross section of the support when the surface of the system support has been subjected to so-called dimple processing. FIG. 40 shows a microwave glow discharge method for forming a light receiving layer of the electrophotographic light receiving member of the present invention. FIG. 41 is a schematic explanatory view of a deposition apparatus when using, FIG. 41 is an example of an apparatus for forming a light receiving layer of a light receiving member for electrophotography of the present invention, which is a manufacturing apparatus by a glow discharge method using microwaves. FIG. 42 is a schematic explanatory view of an example of an apparatus for forming a light receiving layer of the light receiving member for electrophotography of the present invention, and is a schematic explanatory view of a manufacturing apparatus by an RF sputtering method. ... Light receiving member for electrophotography of the present invention 101. Aluminum support 102... Light receiving layer 103... Lower layer 104... Upper layer 105. Light receiving member 201 for aluminum support 202 Photosensitive layer 203 made of A-Si 203 free surface In FIG. 37, 1000 deposition apparatus 1001 by RF glow discharge decomposition method 1001 deposition chamber 1005 cylindrical aluminum-based support 1008 gas introduction pipe 1009 … Gas discharge holes 1012… High frequency matching box 1014… Heating 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 ……………………………………………………………………………………………………………………………………… possible Source pressure gas cylinders 1071 to 1077 In FIG. 41, 1100: a deposition apparatus 1101 by a microwave glow discharge method ... a deposition chamber 1102 ... a derivative window 1103 ... a waveguide 1107 ... a cylindrical aluminum-based support 1109 ... plasma generation Area 1010: Gas introduction pipe In FIG. 42, 1401: Deposition chamber 1402: Cylindrical aluminum support 1405: Target 1407: Main valve 1408 to 1410: Source gas cylinder 1412 to 1414: Mass flow controller 1416 ~ 1418 ... Gas inflow valve 1420 ~ 1422 ... Gas outflow valve 1432 ... Auxiliary valve 1433 ... High frequency matching box 1435 ... Vacuum gauge 1500 ... Material gas supply device 1501 ... Deposition device by RF sputtering method

Continued on the front page (72) Inventor Toshimitsu Kariya 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Hiroaki Shinno 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-62-15554 (JP, A) JP-A-59-212845 (JP, A)

Claims (4)

(57) [Claims] 1. A light-receiving member having an aluminum-based support and a light-receiving layer having a multi-layered structure having photoconductivity on the support, wherein the light-receiving layer is at least aluminum as a constituent element from the support side. Atoms, silicon atoms, hydrogen atoms, a lower layer composed of an inorganic material containing magnesium atoms and having a portion containing the aluminum atoms, silicon atoms, and hydrogen atoms in a non-uniform distribution in the layer thickness direction; The base material is composed of a non-single-crystalline material containing at least one of a hydrogen atom and a halogen atom, and has an upper layer containing atoms for controlling conductivity in a layer region in contact with the lower layer. A light receiving member characterized by the above-mentioned. 2. The light-receiving member according to claim 1, wherein the atom controlling conductivity is an atom belonging to Group III of the periodic table. 3. The light-receiving member according to claim 1, wherein the atoms controlling the conductivity are atoms belonging to Group V of the periodic table excluding nitrogen atoms. 4. The light-receiving member according to claim 1, wherein the atoms that control the conductivity are atoms belonging to Group VI of the periodic table excluding oxygen atoms.