JP2603268B2 - Light receiving member - Google Patents

Description

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

(Prior art)

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

Based on such a point, amorphous silicon (hereinafter referred to as A-Si) is a photoconductive material that has recently attracted attention. For example, German Patent Publication Nos. 2746967 and 2855718.
Japanese Patent Application Laid-Open Publication No. HEI 9-26139 describes an application as a light receiving member for electrophotography.

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 about one digit, 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, and reduces cracks 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 (Al) and silicon atoms (S
i), an inorganic material containing a hydrogen atom (H) and a copper atom (Cu) (hereinafter abbreviated as “AlSiH”), wherein the aluminum atom (Al), silicon atom (Si) and hydrogen atom (H) are 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) Amorphous materials (hereinafter “A-Si
(H, X). " Incidentally, what is commonly called a microcrystalline material is classified as A-Si (H, X)) or a polycrystalline material (hereinafter abbreviated as "poly-Si (H, X)") or both. Including non-single crystalline materials (hereinafter “Non-Si
(Abbreviated as “(H, X)”), and contains at least one of carbon atoms (C), nitrogen atoms (N), and oxygen atoms (O) in a layer region in contact with the lower layer. It is characterized by comprising an upper 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 (Al), silicon atoms (Si), and especially hydrogen atoms (H) in the lower layer in a non-uniform distribution state in the layer thickness direction, the aluminum-based support and the upper layer Injection of charges (photocarriers) between the layers is improved, and furthermore, the systematic structural continuity of the constituent elements between the aluminum-based support and the upper layer is improved, so that image characteristics such as gasket and spot are improved. Is improved, a halftone is clearly output, and a high-quality image with high resolution can be stably repeated.

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 containing copper atoms (Cu) in the lower layer, the injection property and adhesion of electric charges (photocarriers) between the aluminum-based support and the upper layer are improved. Since the traveling property of the electric charge (photocarrier) in the lower layer is remarkably improved, there is a feature that a remarkable improvement is observed in image characteristics and durability.

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

JP-A-59-28162 mentions that aluminum atoms (Al) 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 accompanying drawings.

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

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

Support Aluminum-based support 101 used in the present invention
, An aluminum alloy is used. In the aluminum alloy of the present invention, there is no particular limitation on the alloy components including the base aluminum, and the types and compositions of the components can be arbitrarily selected. Therefore, the aluminum alloy of the present invention is standardized or registered as a wrought material, for casting, die casting, etc. according to Japanese Industrial Standards (JIS), AA Standard, BS Standard, DIN Standard, International Alloy Registration, etc. Aluminum, Al-Cu, Al-Mn,
Alloys with compositions such as Al-Si, Al-Mg, Al-Mg-Si, Al-Zn-Mg, etc., Al-Cu-Mg (duralumin, super duralumin, etc.), Al-Cu-Si (Lautar, etc.), Al-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 the pure aluminum system include, for example, JIS1100 of 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 Al 99.00% by weight or more.

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

As an Al-Mn type, for example, JIS3003, Si 0.6% by weight
Below, Fe 0.7% by weight or less, Cu 0.05-0.20% by weight, Mn 1.
0 to 1.5% by weight, Zn 0.10% by weight or less, and the balance of Al.

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

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

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

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

As an Al-Mg-Si system, for example, JIS6063, Si 0.20 ~
0.6 wt%, Fe 0.35 wt% or less, Cu 0.10 wt% or less, M
n 0.10 wt% or less, Mg 0.45 to 0.9 wt%, Zn 0.10 wt% or less, Cr 0.10 wt% or less, Ti 0.10 wt% or less, Al
The remainder is mentioned.

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

To select the composition of the aluminum alloy in the present invention, as properties according to the purpose of use, for example, mechanical strength,
It may be appropriately selected in consideration of corrosion resistance, workability, heat resistance, dimensional accuracy, etc. For example, 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 (Al), silicon atoms (Si), hydrogen atoms (H), and copper atoms (Cu) as components, and has durability as required. (CNO _c ), atom (M _c ) for adjusting image quality, halogen atom (X), germanium atom (Ge), tin atom (Sn), and magnesium atom (Mg).

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

Copper atoms (Cu) contained in the lower layer and germanium atoms (Ge) and tin atoms (S
n) and atoms for adjusting durability (CNO _c ), atoms for adjusting image quality (M _c ), halogen atoms (X), and magnesium atoms (Mg) are distributed uniformly throughout the entire lower layer. It may be contained in a state, or may be contained evenly in the entire layer region of the lower layer, but may have a part contained in a state of being unevenly 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 contained evenly and without unevenness from the viewpoint of achieving uniform characteristics in the in-plane direction.

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

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

FIGS. 3 to 8 show the aluminum atoms (A) contained in the lower layer of the electrophotographic light-receiving member of the present invention.
l), copper atoms (Cu), and germanium atoms (Ge) and tin atoms (Sn), which are contained as necessary, atoms for adjusting durability (CNO _c ), and atoms for adjusting image quality (M _c )
And a halogen atom (X) and a magnesium atom (M
A typical example of the distribution state in the layer thickness direction of g) is shown.

3 to 8, the abscissa represents an aluminum atom (Al) (hereinafter abbreviated as “atom (Al)”), a copper atom (C
u) (hereinafter abbreviated as “atom (Cu)”), magnesium atom (Mg) (hereinafter abbreviated as “atom (Mg)]), germanium atom (Ge) and tin atom (Sn) (hereinafter“ atom (G
Abbreviated as “S _c )”), an atom that adjusts durability (CNO _c )
(Hereinafter abbreviated as “atom (CNO _c )”), atoms for adjusting image quality (M _c ) (hereinafter abbreviated as “atom (M _c )”), halogen atoms (X) (hereinafter “atom (X)”) Abbreviated to the atom (A
l), atom (Cu), atom (Mg), atom (GS _c ), and atom (C
NO _c ), atom (M _c ), and atom (X) are collectively referred to as “atom (AC
u) ". However the layer thickness direction of the distribution of atoms (Al) and atoms (Cu) and atoms (Mg) and atoms (GS _c) and atoms (CNO _c) and atoms (M _c) and atoms (X) may be the same the distribution density C also may be said), 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 upper layer side of the lower layer Indicates the position of the end face. That is, the atom (AC
lower layer contained in u) 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 (ACu) 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 (ACu) 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 (ACu) 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 (ACu) gradually decreases continuously from the concentration C ₅₁ up to the position t _T to the position t _B, the concentration at position t _T forming a kind of distribution becomes C _52.

In the example shown in Figure 6, the distribution concentration C of the atoms contained (ACu) 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 (ACu) 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 contained atoms (ACu) gradually and continuously decreases from the concentration C ₈₁ from the position t _B to the position t _T , and at the position t _T forming a kind of distribution becomes C _82.

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

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

FIGS. 9 to 16 show silicon atoms (Si) contained in the lower layer of the electrophotographic light-receiving member of the present invention;
Hydrogen atom (H), copper atom (Cu), magnesium atom (Mg), germanium atom (Ge) contained as necessary,
A typical example of a distribution state of a tin atom (Sn), an atom (CNO _c ), an atom (M _c ), and a halogen atom (X) in a layer thickness direction is shown.

9 to 16, the horizontal axis is a silicon atom (S
i), a hydrogen atom (H), a copper atom (Cu), magnesium atom (Mg), atom (GS _c), atoms (CNO _c), atom (M _c),
Atom (X) (hereinafter collectively referred to as "atom (SHCu)". However, silicon atom (Si), hydrogen atom (H), copper atom (Cu), magnesium atom (Mg), and atom (GS _c ), atoms (CNO _c ), atoms (M _c ), and atoms (X) in the layer thickness direction may be the same or different), and the vertical axis indicates the lower layer. denotes a layer thickness of, t _B is the position of the end face of the lower layer on the support side, t _T represents the position of the end face of the lower layer of the upper layer side. That is, the lower layer contained the atoms (SHCu) is a layer formed toward the t _T side from t _B side.

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

In the example shown in FIG. 9, the distribution concentration C of the contained atoms (SHCu) increases linearly 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. 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 (SHCu) until 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 (SHCu), 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 atoms contained (SHCu), the concentration C ₁₂₁ up to the position t ₁₂₁ to the position t _B
A linear function increasing to next concentration C ₁₂₂ at position t ₁₂₁ 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 atoms contained (SHCu), the concentration C ₁₃₁ up to the position t ₁₃₁ to the position t _B
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 (SHCu) gradually and continuously increases from the concentration C ₁₄₁ from the position t _B to the position t _T , and the concentration C 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 (SHCu) 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 (SHCu) includes a concentration C ₁₆₁ at position t _T is gradually increased from substantially zero up to the position t _T to the position t _B A distribution state is formed as follows.

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

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

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

In the present invention, by containing copper atoms (Cu) in the lower layer, the effect of improving the charge injection property mainly between the aluminum-based support and the upper layer and / or
Alternatively, it is possible to obtain the effect of improving the traveling property of the electric charge in the lower layer and / or the effect of improving the adhesion between the aluminum-based support and the upper layer. The content of copper atoms (Cu) 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, Preferably 1 × 10 ² to 1 × 10 ⁵ atomic ppm, most preferably 5 × 10 ^{2 to} 5 × 10
Desirably, it is ⁴ atomic ppm.

The effect of improving the charge injection property between the aluminum-based support and the upper layer mainly by containing magnesium atoms (Mg) in the lower layer as needed, and / or the mobility of the charge in the lower layer And / or an effect of improving the adhesiveness between the aluminum-based support and the upper layer. 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 atoms p.
pm, more preferably 1 × 10 ² to 1 × 10 ⁵ atomic ppm, and most preferably 5 × 10 ^{2 to} 5 × 10 ⁴ atomic ppm.

By allowing the lower layer to contain germanium atoms (Ge) and / or tin atoms (Sn) as necessary,
The effect of improving the charge injection property mainly between the aluminum-based support and the upper layer and / or the effect of improving the charge transportability in the lower layer and / or 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 (Al) is small. 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, but is preferably 1 to 9 × 10 ⁵ atomic ppm, more preferably 1 × 10 ² to 8 × 1
0 ⁵ atomic ppm, being the optimal ⁵ × 10 ² ~7 × 10 5 atomic ppm is desirable.

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). It mainly compensates for dangling bonds, such as silicon atoms (Si) and aluminum atoms (Al), contained in the lower layer, and makes it possible to improve the layer quality by stabilizing the structure and structure. 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 (Al) 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.

The atoms (M _c ) for adjusting the image quality contained as required include atoms belonging to Group III of the periodic table excluding aluminum atoms (Al) (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 Tl (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. Further, in the layer region where the content of aluminum atoms (Al) is small in the lower layer, the effect of controlling the conductivity type and / or conductivity can be obtained. The content of atoms (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 AlSiH is created, for example, by the same vacuum deposition film forming method as the upper layer described later, by appropriately setting the numerical conditions of the film forming parameters so as to obtain desired characteristics. You. Specifically, for example, glow discharge method (AC discharge CVD such as low frequency CVD, high frequency CVD or microwave CVD, or DC discharge CVD, etc.), ECR
-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 the electrophotographic light-receiving member having characteristics, and it is easy to introduce hydrogen atoms (H) together with aluminum atoms (Al) 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 AlSiH by a glow discharge method, an Al supply gas capable of supplying aluminum atoms (Al) and a silicon atom (S
i) a gas for supplying Si, a gas for supplying H that can supply hydrogen atoms (H), and a gas for supplying copper atoms (Cu).
A feed gas, and Mg-feeding gas capable of feeding the magnesium atom (Mg), if necessary with GS _c-feeding gas capable of supplying germanium atoms (Ge) and tin atoms (Sn) if necessary, X supply gas that can supply halogen atoms (X) as needed, CNO _c supply gas that can supply atoms (CNO _c ) to adjust durability as needed, and image quality as needed An M _c supply gas capable of supplying atoms (M _c ) to be adjusted is introduced at a desired gas pressure state into a deposition chamber in which the inside can be reduced in pressure, and a glow discharge is generated in the deposition chamber. On a given support surface
What is necessary is just to form the layer which consists of AlSiH.

In order to form the lower layer composed of AlSiH by the HRCVD method, basically, an Al supply gas that can supply aluminum atoms (Al) and a Si that can supply silicon atoms (Si)
Supply gas, Cu supply gas that can supply copper atoms (Cu), and magnesium atoms (Mg) as needed
Mg supply gas and, if necessary, germanium atoms (Ge)
And GS _c-feeding gas capable of feeding a tin atom (Sn) and,
X supply gas that can supply halogen atoms (X) as needed, CNO _c supply gas that can supply atoms (CNO _c ) to adjust durability as needed, and image quality as needed The gas for supplying the M _c, which can supply the atoms to be adjusted (M _c ), can be supplied separately or together as necessary to a desired gas pressure state in the activation space provided at the preceding stage in the deposition chamber where the inside can be reduced in pressure. To generate an active species (A) by generating a glow discharge in the activation space or by heating, and separate an H supply gas capable of supplying a hydrogen atom (H). To form an active species (B), and the active species (A) and the active species (B) are separately introduced into the deposition chamber, respectively. What is necessary is just to form a layer made of AlSiH on the surface of the support.

In order to form the lower layer composed of AlSiH by FOCVD method, basically, aluminum atoms (Al) can be supplied
Al supply gas, Si supply gas capable of supplying silicon atoms (Si), H supply gas capable of supplying hydrogen atoms (H), and Cu supply gas capable of supplying copper atoms (Cu) , and Mg-feeding gas capable of feeding the magnesium atom (Mg), if necessary with GS _c-feeding gas capable of supplying germanium atoms (Ge) and tin atoms (Sn) optionally, if desired An X supply gas capable of supplying a halogen atom (X) and an atom (CNO _c ) for adjusting durability as required can be supplied
The CNO _c supply gas and the M _c supply gas that can supply atoms (M _c ) for adjusting the image quality as needed are separately or together as needed in a deposition chamber where the inside can be evacuated. 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 AlSiH 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 Al, a target composed of Si, or a target composed of Al and Si in an atmosphere of an inert gas such as He or a mixed gas based on these gases. And an H supply gas capable of supplying hydrogen atoms (H), a Cu supply gas capable of supplying copper atoms (Cu), and a Mg supply gas capable of supplying magnesium atoms (Mg) as necessary And a gas for supplying G _Sc that can supply germanium atoms (Ge) and tin atoms (Sn) as needed, and X that can supply halogen atoms (X) as needed.
Supply gas and, if necessary, atoms to adjust durability (CN
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 Al supply gas that can supply aluminum atoms (Al) 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 formed. 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 accommodated 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). 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, at the time of forming the lower layer, aluminum atoms (Al), silicon atoms (Si), hydrogen atoms (H), copper atoms (Cu), and optionally magnesium contained in the lower layer are formed. Atoms (Mg) and germanium atoms (Ge)
And tin atom (Sn), halogen atom (X), atom for adjusting durability (CNO _c ), and atom for adjusting image quality (M _c ) (hereinafter, these are collectively abbreviated as “atom (ASH)”) In order to form a layer having a desired distribution state (depth profile) in the layer thickness direction by changing the distribution concentration C in the layer thickness direction, in the case of the glow discharge method, the HRCVD method, and the FOCVD method, the distribution concentration This is achieved by introducing an atomic (ASH) supply gas whose gas flow rate is to be changed into a deposition chamber by appropriately changing the gas flow rate according to a desired change rate 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, a target for sputtering, for example, Al
If you use a target mixed with Si and
This is achieved by changing the mixing ratio of Al and Si in the thickness direction of the target in advance.

Examples of the substance that can be the Al supply gas used in the present invention include AlCl ₃ , AlBr ₃ , AlI ₃ , Al (CH ₃ ) ₂ Cl, Al (CH ₃ ) ₃ , A
l (OCH ₃ ) ₃ , Al (C ₂ H ₅ ) ₃ , Al (OC ₂ H ₅ ) ₃ , Al (iC ₄ H ₉ ) ₃ , Al (iC ₃ H
₇ ) ₃ , Al (C ₃ H ₇ ) ₃ , Al (OC ₄ H ₉ ) _{3 and the} like can be used effectively. Further, these Al 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. .

To structurally introduce copper atoms (Cu) into the lower layer,
In forming the layer, a raw material for supplying copper atoms (Cu) may be introduced in a gaseous state into the deposition chamber together with another raw material for forming the lower layer. As a material that can be used as a raw material for supplying copper atoms (Cu), a material that is gaseous at ordinary temperature and normal pressure or that can be easily gasified at least under layer forming conditions is preferably used.

Copper atom (Cu) is a substance that can be used as a Cu supply gas.
The organic metal containing is effectively used. In particular, bisdimethylglyoximato copper (II) Cu (C)
₄ H ₇ N ₂ O ₂ ) ₂ is preferred.

In addition, these Cu 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 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 Ne 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 Cl ₂ , GeH _{3
Cl, GeHBr 3, GeH 2 Br} 2, GeH 3 Br, GeHI 3, GeH 2 I 2, GeH 3 hydrogenated germanium halide of I, _{etc., GeF 4, GeCl 4, GeBr} 4, GeI 4,
Substances in the gaseous state or gasifiable substances such as germanium halides such as 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 , SnH ₃ C
1, SnHBr ₃ , SnH ₂ Br ₂ , SnH ₃ Br, SnHI ₃ , SnH ₂ I ₂ , SnH ₃ I, etc.Hydrogen halide tin, SnF ₄ , SnCl ₄ , SnBr ₄ , SnI ₄ , SnF ₂ , SnC
Substances in the gaseous state or gasifiable substances such as tin halides such as l ₂ , SnBr ₂ and SnI ₂ can also be mentioned as effective starting materials for forming the lower layer.

Also, depending on these GS _C feed gas required H _2, the He,
It may be diluted with a gas such as Ar or Ne before use.

In order to structurally introduce the halogen atoms (X) into the lower layer, a raw material for supplying the halogen atoms (X) is formed in a gaseous state in the deposition chamber during the layer formation. 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 and being in a gaseous state or capable of being gasified and having 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 , IBr and the like.

As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, silicon halides such as SiF ₃ , 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 AlSiH 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, and other halogenated compounds such as HF, HCl, HBr, and Hl are used. Hydrogen, SiH ₃ F, SiH
_{2 F 2, SiHF 3, SiH} 2 I 2, SiH 2 Cl 2, SiHCl 3, SiH 2 Br 2, SiHBr halogenated silicon hydride, lower layer or material is also enabled that can be gasified in like gaseous state, such as ₃ It can be mentioned as a raw material for formation.

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 include boron hydrides such as B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ and BBr ₃ . In addition, GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , T
lCl _{3 and the} like can also be mentioned.

As a raw material for supplying a group V atom, in the present invention, it is preferable to use PH ₃ ,
P ₂ H _4, etc. of hydrogen phosphorus _{halides, PH 4 I, PF 3,} PF 5, PCl 3, PCl 5, PBr 3, PBr
_5, a halogenated phosphorus PI ₃ and the like. In addition, AsH ₃ , As
F ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF 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 ₄ H ₄ S,
Substances in a gaseous state or capable of being gasified, such as (CH ₃ ) ₂ S and (C ₂ H ₅ ) ₂ S, are mentioned. In addition, SeH ₂ , SeF ₆ , (CH ₃ ) ₂ Se, (C ₂ H
₅ ) Substances in a gaseous state or capable of being gasified, such as 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.

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 ₃ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), and 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), as the acetylenic hydrocarbon, acetylene (C ₂ H ₂₎ , methylacetylene (C ₃ H _4), butyne (C ₄ H _6), and the like.

In addition, CF ₄ , CCl ₄ , and CH ₃ can be supplied in addition to supplying 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, for example, nitrogen (N ₂ ), 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, in addition to the supply of nitrogen atoms (N), the supply of halogen atoms (X) can also 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 tetraoxide (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 (Al) of the lower layer.
Is a region in which the content of aluminum atoms is 95% or less of the content of aluminum atoms (Al) in the aluminum-based support. This means that the aluminum atom (Al) content is 95% of the aluminum atom (Al) content in the aluminum-based support.
This is because, in the region of the composition exceeding, the function has almost only the function of the support. Further, the end face of the lower layer with the upper layer is a region where the content of aluminum atoms (Al) in the lower layer exceeds 5%. This is because, in a region having a composition in which the content of aluminum atoms (Al) is 5% or less, almost all of the functions have only the function of the upper layer.

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

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

The support temperature (Ts) is appropriately selected in an optimum range according to the layer design, but is usually 50 to 600 ° C., preferably 100 to 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 the carbon layer (C) and / or the nitrogen atom (N) and / or the oxygen atom (O) are contained in at least the layer region of the upper layer in contact with the lower layer in the present invention, and the conductivity is controlled as necessary. May also be contained,
Neither germanium 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).

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

At least a layer (M), a carbon atom (C), a nitrogen atom (N), an oxygen atom (O), a germanium atom (G
e), when containing at least one of tin atoms (Sn), the above-mentioned conductivity controlling atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), germanium atoms ( Ge) and tin atoms (Sn) may be uniformly distributed in the layer region, or may be uniformly distributed in the layer region, but may be unevenly distributed in the layer thickness direction. Some parts may be contained in a distributed state.

However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary to be contained evenly and evenly from the viewpoint of achieving uniform characteristics in the in-plane direction. .

Further, the upper layer in the present invention may contain copper atoms (Cu). When copper atoms (Cu) are contained in the upper layer, they may be contained in the entire layer region of the upper layer, or may be contained in some layer regions of the upper layer. In any case, Copper atoms (Cu) may be uniformly distributed in the layer region, or may be uniformly distributed in the layer region, but may be unevenly distributed in the layer thickness direction. May be present.

However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary to be uniformly contained in a uniform distribution from the viewpoint of achieving uniform characteristics in the in-plane direction. .

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 uniformly contained in a uniform distribution from the viewpoint of achieving uniform characteristics in the in-plane direction. .

Further, a layer region (hereinafter abbreviated as “layer region (M)”) containing atoms (M) (hereinafter, abbreviated as “atom (M)”) for controlling conductivity, a magnesium atom (Mg) (hereinafter, abbreviated as “layer region (M)”). Layer region (hereinafter abbreviated as “layer region (Mg)”) containing copper atoms (Cu) (hereinafter abbreviated as “atom (Cu)”). (Hereinafter abbreviated as “layer region (Cu)”) contains carbon atoms (C) and / or nitrogen atoms (N) and / or oxygen atoms (O) (hereinafter abbreviated as “atoms (CNO)”). A layer region (hereinafter abbreviated as “layer region (CNO _B )”) that is in contact with at least the lower layer of the upper layer to be formed may be substantially the same layer region, or at least the surface of the layer region (CNO _B ) Part of the side may be shared, or may be inherent in the layer region (CNO _B ).

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

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

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, layer A typical example of the distribution of atoms (Mg) in the region (Mg) in the layer thickness direction, and a typical example of the distribution of atoms (Cu) in the layer region (Cu) in the layer thickness direction are shown. It is a thing. (Hereafter, layer area (M),
The layer region (CNO), the layer region (GS), the layer region (Mg), and the layer region (Cu) are represented as “layer region (Y)”, and the atom (M), the atom (CNO), and the atom (GS ), Atoms (Mg) and atoms (Cu) are represented as “atoms (Y)”. Therefore, the seventeenth
FIGS. 36 to 36 show the atoms (Y) contained in the layer region (Y).
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), the layer region (Mg), and the layer region ( When Cu) is substantially the same layer region, the layer region (Y) is singularly included in the upper layer, and when not substantially the same layer region, the layer region (Y) is included in the upper layer. Are included multiple times).

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 linear function manner up to the position t ₁₈₁ to the position t _B From the position t ₁₈₁ to the position t _T, a distribution state is formed such that the density C ₁₈₃ takes a constant value.

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

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

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

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

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

In the example shown in FIG. 24, the concentration to the distribution concentration C of the atoms contained (Y) leads to a position t _T to the position t ₂₄₁ becomes a constant value consisting concentration C ₂₄₁ than to the position t ₂₄₁ position t _B gradually decreases continuously from 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 Concentration C ₂₆₁
And linearly decreases to a form a kind of distribution that the concentration C ₂₆₂ at position t _T.

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

In the example shown in FIG. 28, the distribution concentration C of the atoms contained (Y) is, 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 Concentration C ₂₈₁
And linearly decreases to a form a kind of distribution that the concentration C ₂₈₂ at position t _T.

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

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

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

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

In the example shown in FIG. 33, the distribution concentration C of the atoms contained (Y) is substantially 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 ,
The distribution state is such that the density C ₃₃₂ takes a constant value from the position t ₃₃₁ to the position t _T.

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

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

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

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

In the present invention, the carbon atom (C) is added to the layer region (CNO).
And / or the inclusion of nitrogen atoms (N) and / or oxygen atoms (O) to increase the dark resistance and / or hardness and / or control the spectral sensitivity and / or the layer area (CNO _B ). The effect of improving adhesion between the lower layer and / or improving adhesion between the layer region (CNO) and the layer region of the upper layer other than the layer region (CNO) can be obtained.

Carbon atoms (C) contained in the layer region (CNO) and / or
Alternatively, the content of nitrogen atoms (N) and / or oxygen atoms (O) is preferably 1 to 9 × 10 ⁵ atomic ppm, more preferably 1 × 10 ^{1 to} 5 × 10 ⁵ atomic ppm, and most preferably 1 × 10 5 to 10 × 10 ⁵ atomic ppm. 10 ² 〜
Desirably, it is 3 × 10 ⁵ atomic ppm. In particular, when high dark resistance and / or high hardness are measured, preferably 1 ×
The concentration is preferably 10 ^{3 to} 9 × 10 ⁵ atomic ppm, and preferably 1 × 10 ^{2 to} 5 × 10 ⁵ atomic ppm when controlling the spectral sensitivity.
It is desirable to be ppm.

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

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 more preferably 5 × 10 ^{-2 to} 5 × 10 ² atomic ppm.

In the present invention, the copper atom (C
The content of u) is preferably 1 × 10 ⁻³ to 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 is desirably set to 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) Supplying Ge supply gas capable of supplying atoms (Ge) and / or Sn supply gas capable of supplying tin atoms (Sn), Mg supply gas capable of supplying magnesium atoms (Mg), and copper atoms (Cu) Gas that can be supplied to the inside Introduced into the chamber at a desired gas pressure to generate a glow discharge in the deposition chamber,
A layer made of Non-Si (H, X) may be formed on the surface of the support on which a predetermined lower layer has been formed, which is previously set at a predetermined position.

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. Supply gas to be obtained, and M supply gas to supply atoms (M) for controlling conductivity and / or C supply gas to supply carbon atoms (C) and / or nitrogen atoms (N ) And / or an O supply gas that can supply oxygen atoms (O) and / or a Ge supply gas and / or tin atoms (Sn) that can supply germanium atoms (Ge). Sn supply gas that can be supplied,
A Mg supply gas that can supply magnesium atoms (Mg) and a Cu supply gas that can supply copper atoms (Cu) can be separately or together, if necessary, at the front stage of the deposition chamber where the inside can be reduced in pressure. The activated species are introduced into the activated space under a desired gas pressure state, and a glow discharge is generated or heated in the activated space to generate an active species (A), and a hydrogen atom (H) is generated. The H supply gas that can be supplied is similarly introduced into another activation space to generate an active species (B), and the active species (A) and the active species (B) are separately introduced into the deposition chamber. A layer made of Non-Si (H, X) may be formed on the surface of the support on which a predetermined lower layer has been formed, which is previously set at a predetermined position.

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 capable of supplying magnesium atoms (Mg) and Cu supply gas capable of supplying copper atoms (Cu) are separately or together as required in a deposition chamber capable of reducing the pressure inside. The gas is introduced under a gas pressure state, and further, a halogen (X) gas is introduced into the deposition chamber at a desired gas pressure state separately from the supply gas, and these gases are chemically reacted in the deposition chamber. Non-Si (H, H,
X) may be formed.

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

In the present invention, when the upper layer is formed, atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), and germanium atoms (G) that control conductivity contained in the upper layer are formed.
e), the distribution concentration C of tin atoms (Sn), magnesium atoms (Mg), and copper atoms (Cu) (hereinafter collectively referred to as “atoms (Z)”) is changed in the layer thickness direction, In order to form a layer having a desired distribution in the thickness direction (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 This is achieved by appropriately changing the gas flow rate according to a desired change rate curve and introducing the gas into the deposition chamber.

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

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 raw material gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

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

Further, in the present invention, a silicon hydride compound containing a halogen atom (X), which is a gas state containing a silicon atom (Si) and a halogen atom (X) as constituent elements or which can be gasified, is also considered to be effective. Can be mentioned.

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

As a silicon compound containing a halogen atom (X), that is, a silane derivative substituted with a so-called halogen atom (X), specifically, for example, silicon halide such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ is used. It can be mentioned as preferred.

When a silicon compound containing a halogen atom (X) is used to form the 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.

When forming an upper layer containing a halogen atom (X) according to a glow discharge method or an HRCVD method, basically,
For example, an upper layer can be formed on a desired support by using silicon halide as a gas for supplying Si. However, in order to make the introduction ratio of hydrogen atoms (H) easier, These gases 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, but 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 , SiHCl ₃ , SiH ₂ B
Halogen-substituted silicon hydrides such as r 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, it is also possible to cause discharge by causing H ₂ or silicon hydride such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ to coexist with the aforementioned Si supply in the deposition chamber. It can be carried out.

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 introduced 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 ,
Examples include boron hydrides such as B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InC
l ₃ , TlCl _{3 and the} like can also be mentioned.

As a raw material for supplying a group V atom, in the present invention, it is preferable to use PH ₃ ,
P ₂ H _4, etc. of hydrogen phosphorus _{halides, PH 4 I, PF 3,} PF 5, PCl 3, PCl 5, PBr 3, PBr
_5, a halogenated phosphorus PI ₃ and the like. In addition, AsH ₃ , As
F ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF 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, C 4 H
Substances in a gaseous state or capable of being gasified, such as ₄ S, (CH ₃ ) ₂ S and (C ₂ H ₅ ) ₂ S, are mentioned. In addition, SeH ₂ , SeF ₆ , (CH ₃ ) ₂ Se, (C
_{2 H 5) 2 Se, TeH} 2, TeF 6, (CH 3) 2 Te, include (C ₂ H ₅₎ may or gasified gas state such as ₂ Te material.

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 raw material 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.
4 ethylene-based hydrocarbons, and acetylene-based hydrocarbons having 2 to 3 carbon atoms.

Specifically, as the saturated hydrocarbon, methane (C
H ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), and 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), as the acetylenic hydrocarbon 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 carbon atoms (C), because halogen atoms (X) can be supplied.
A halogenated carbon gas such as CF ₃ can be used.

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, in addition to the supply of nitrogen atoms (N), the supply of halogen atoms (X) can also 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 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 tetroxide (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 layers making work readiness in 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 Cl ₂ , GeH _{3
Cl, GeHBr 3, GeH 2 Br} 2, GeH 3 Br, GeHI 3, GeH 2 I 2, GeH 3 hydrogenated germanium halide of I, _{etc., GeF 4, GeCl 4, GeBr} 4, GeI 4,
_{GeF 2, GeCl 2, GeBr 2} , can be exemplified GeI ₂ like germanium halide or a substance capable of gasification of so gaseous state also as an effective starting material for the upper 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 the layer forming operation and good Sn supply efficiency.

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

To structurally introduce copper atoms (Cu) into the upper layer,
In forming the layer, a raw material for supplying copper atoms (Cu) may be introduced in a gas state into the deposition chamber together with other raw materials for forming the upper layer. As a material that can be used as a raw material for supplying copper atoms (Cu), 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.

Copper atom (Cu) is a substance that can be used as a Cu supply gas.
The organic metal containing is effectively used. In particular, in view of the easiness of handling at the time of forming a layer and the good supply efficiency of Cu, etc., bisdimethylglyoximato copper (II) Cu (C ₄ H
₇ N ₂ O ₂ ) ₂ is preferred.

In addition, these Cu 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 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.

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

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

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

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 increase the temperature of the support, specifically 40
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 layer formation factors are not usually independently determined separately, but are optimally determined based on mutual and organic relationships to form an upper layer having desired characteristics. It is desirable to decide.

〔Example〕

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

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

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

In the closed container of the gas cylinders 1078, 1080 of 1071, 1072, 1073, 1074, 1075, 1076, 1077, 1079 in the figure, the source gas for forming each layer of the present invention is sealed, and 1071 is
SiH ₄ gas (purity 99.99%) cylinder, 1072 is H ₂ gas (purity 9
9.9999%) cylinder, 1073 is a CH ₄ gas (purity 99.999%) cylinder, 1074 is a GeH ₄ gas (purity 99.999%) cylinder, 1075 is
H ₂ gas in the diluted B ₂ H ₆ gas (99.999% purity, hereinafter "B ₂
H ₆ / H ₂ ), 1076 is NO gas (purity 99.9999
%) Cylinder, 1077 and 1079 are He gas (99.999% purity) cylinders, 1078 is a sealed container filled with AlCl ₃ (99.99% purity), and 1080 is Cu (C ₄ H ₇ N ₂ O ₂ ) 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, valves 1051 to 105 of gas cylinders 1071 to 1077 and 1079
8, Inflow valves 1031-1038, Leak valve 1 of deposition chamber 1001
Make sure 015 is closed and
After confirming that the auxiliary valve 1018 was open at 041 to 1048, the main valve 1016 was first opened, and the inside of the deposition chamber 1001 and the gas pipe were evacuated by a vacuum pump (not shown).

Next, when the reading of the vacuum gauge 1017 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, GeH ₄ gas from gas cylinder 1074, B ₂ H ₆ / H ₂ gas from gas cylinder 1075, NO gas from gas cylinder 1076, gas cylinder 1077,1079
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 by Cu (C
₄ H ₇ N ₂ O ₂ ) ₂
Cu (C ₄ H ₇ N ₂ O ₂ ) ₂ gas diluted with gas (hereinafter “Cu (C ₄ H ₇ N ₂
O ₂ ) ₂ / He ”).

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, and Cu (C ₄ H ₇ N ₂ O ₂ ) ₂ / He gas were introduced into the deposition chamber 1001 through the gas discharge holes 1009 of the gas introduction pipe 1008. At this time, the SiH ₄ gas flow rate was 50 SCCM, and the H ₂ gas flow rate was 10 S
The mass flow controllers 1021, 1022, 1027, and 1028 adjusted the flow rates of CCM and AlCl ₃ / He gas to 120 SCCM and the flow rate of Cu (C ₄ H ₇ N ₂ O ₂ ) ₂ / He to 5 SCCM. The opening of the main valve 1016 was adjusted while watching the vacuum gauge 1017 so that the pressure in the deposition chamber 1001 became 0.4 Torr. Then, not shown
The power of the RF power introduced RF power into the deposition chamber 1001 through the high-frequency matching box 1012 is set to 5 mW / cm ^3, to rise to RF glow discharge was initiated to form the lower layer on a cylindrical aluminum base support on . During formation of the lower layer, as the SiH ₄ gas flow rate is constant flow rate of 50 SCCM, H ₂ gas flow rate 10SC
AlCl ₃ / H to increase at a constant rate from CM to 200 SCCM
e The mass flow controllers 1021, 1022, 102 so that the gas flow rate decreases from 120 SCCM to 40 SCCM at a constant rate, and the Cu (C ₄ H ₇ N ₂ O ₂ ) ₂ / He gas flow rate becomes a constant flow rate of 5 SCCM.
7,1028 was adjusted, RF glow discharge was stopped when the lower layer having a thickness of 0.05 μm was formed, and the outflow valves 1041, 1042,
1047, 1048 and the auxiliary valve 1018 are closed, and the deposition chamber 1001 is closed.
The flow of gas into the interior was stopped, 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, 1046 and the auxiliary valve 1018 are gradually opened to open the SiH ₄ gas, H ₂ gas, B ₂ H ₆ / H ₂ Gas and NO gas were caused to flow into the deposition chamber 1001 through the gas discharge holes 1009 of the gas introduction pipe 1008. At this time, SiH ₄ gas flow rate 100 SCCM, H ₂ gas flow rate _{100SCCM, B 2 H 6 / H} 2 gas flow rate relative to the SiF ₄ gas flow rate
The mass flow controllers 1021, 1022, 1025, and 1026 adjusted the flow rates of 800 ppm and NO gas to 10 SCCM.
Vacuum gauge 101 so that the pressure in deposition chamber 1001 becomes 0.4 Torr.
The opening of the main valve 1016 was adjusted while watching 7. After that, the power of the RF power supply (not shown) is set to 10 mW / cm ³ and RF power is introduced into the deposition chamber 1001 through the high-frequency matching box 1012 to generate an RF glow discharge, and the first layer of the upper layer is formed on the lower layer. The formation of the layer region was started. During formation of the first layer region of the upper layer, SiH ₄ gas flow rate 100 SCCM, H ₂ gas flow rate 100SCC
The M, B ₂ H ₆ / H ₂ gas flow rate is constant at 800 ppm with respect to the SiH ₄ gas flow rate, and the NO gas flow rate is 10 SC for the lower layer side 2 μm.
The mass flow controllers 1021, 1022, 1025, and 1026 are adjusted so that the flow rate of CM is reduced at a fixed rate from 10 SCCM to 0 SCCM on the front side 1 μm at the surface side of 1 μm, and the layer thickness is 3 μm.
The RF glow discharge is stopped where the first layer region of the upper layer is formed, and the outflow valves 1041, 1042, 1045, 1046 and the auxiliary valve 1018 are closed to stop the flow of gas into the deposition chamber 1001. Thus, 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. After that, the power of the RF power supply (not shown) was set to 15 mW / cm ³ and RF power was introduced into the deposition chamber 1001 through the high frequency matching box 1012,
An RF glow discharge is generated, a second layer region of the upper layer is formed on the first layer region of the upper layer, and an RF glow discharge is formed when the second layer region of the upper layer having a thickness of 20 μm is formed. Stop, and also set outflow valves 1041 and 1042 and auxiliary valve 1018
Was closed, the flow of gas into the deposition chamber 1001 was stopped, and the formation of the second layer region of the upper layer was completed.

Next, to form the third layer region of the upper layer, the outflow valve 1041, 1043 and the auxiliary valve 1018 are gradually opened to open 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. Vacuum gauge 1017 so that the pressure in the deposition chamber 1001 becomes 0.4 Toor.
While adjusting the opening of the main valve 1016. Thereafter, the power of the RF power source (not shown) by introducing a RF power into the deposition chamber 1001 through the high-frequency matching box 1012 set at 10 mW / cm ^3, to rise to RF glow discharge, the upper layer a second layer region The formation of the third layer region was started, the RF glow discharge was stopped when the third layer region of the upper layer having a thickness of 0.5 μm was formed, and the outflow valves 1041 and 1043 and the auxiliary valve 1018 were formed.
Was closed, the flow of gas into the deposition chamber 1001 was stopped, and the formation of the third layer region of the upper layer was completed.

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

It goes without saying that the outflow valves other than the gas necessary for forming each layer are completely closed, and each gas is supplied to the inside of the deposition chamber 1001 and outflow valves 1041 to 1041.
To avoid remaining in the piping from 1048 to the deposition chamber 1001, the outflow valves 1041 to 1048 are closed and the auxiliary valve 10
Open 18 and then fully open the main valve to evacuate the system once to a high vacuum as needed.

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

<Comparative Example> Photoreceptor for electrophotography under the same preparation conditions as in Example 1 except that H ₂ gas and Cu (C ₄ H ₇ N ₂ O ₂ ) ₂ / He gas were not used when forming the lower layer. Created a member. 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 modified for experiments, and several under various conditions. When the electrophotographic characteristics were checked, no image defects were found even when a high voltage was applied to the electrophotographic light-receiving member due to extremely strong corona charging and frictional charging with a cleaning agent or the like. .

Next, when the number of spots was compared as an image characteristic, in particular, the number of spots having a diameter of 0.1 mm or less was better for the electrophotographic light receiving member of Example 1 than for the electrophotographic light receiving member of Comparative Example.
It turned out that the number of spots was 1/4 or less. Furthermore, in order to compare the degree of roughness, 100 points of image density were measured with a circular area having a diameter of 0.05 mm as one unit,
When the variation of the image density was evaluated, the variation of the electrophotographic light receiving member of Example 1 was 1/5 or less than that of the electrophotographic light receiving member of Comparative Example, and the electrophotographic light receiving member of Example 1 was visually observed. It was found that the light receiving member was superior to the electrophotographic light receiving member of the comparative example.

In addition, in order to compare the degree of occurrence of image defects and the occurrence of peeling of the light-receiving layer due to relatively short-term mechanical pressure applied to the light-receiving member for electrophotography, a diameter of 3.5 mm was used.
The stainless steel ball of Example 1 was dropped freely from 30 cm vertically above the surface of the electrophotographic light-receiving member and was applied to the surface of the electrophotographic light-receiving member, and the probability of cracks in the light-receiving layer was measured. It was found that the probability of occurrence of the photographic light receiving member was 1/5 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, B ₂ H ₆ / H ₂ gas and NO gas were
The method of changing the l ₃ / He flow rate was changed, and a light-receiving member for electrophotography was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 3, and the same evaluation was performed. In addition, a good effect of improving spotting, roughening, and layer peeling was obtained.

Example 3 In the lower layer, a gas obtained by diluting Mg (C ₅ H ₅ ) ₂ gas with He gas from a closed container (not shown) (hereinafter abbreviated as “Mg (C ₅ H ₅ ) ₂ / He”) was used. , GeH ₄ gas, He gas from a cylinder (not shown) in the upper layer, and CH ₄ gas not used. A light-receiving member was prepared and evaluated in the same manner. As in Example 1, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 4> (not shown) of the sealed container from _{Mg (C 5 H 5) 2} / He gas, CH ₄ gas, B ₂
H ₆ / H ₂ gas, NO gas, SiF ₄ gas (purity 99.999%) from a cylinder (not shown), and N ₂ gas and He gas from a cylinder (not shown) were further 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 good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 5> In the upper layer, an H ₂ gas cylinder was replaced with an Ar gas cylinder (purity 9).
9.9999%), the CH ₄ gas cylinder was changed to an NH ₃ gas cylinder (purity: 99.999%), SiF ₄ gas was further used, and the light-receiving member for electrophotography was used in the same manner as in Example 1 under the preparation conditions shown in Table 6. Was prepared and evaluated in the same manner. As in Example 1, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 6> CH ₄ gas and B ₂ H ₆ / H ₂ gas were further used in the lower layer, and PH ₃ / H ₂ gas (purity: 99.999%) was further used in the upper layer from a cylinder (not shown). Under the conditions shown in Table 7, a light receiving member for electrophotography was prepared in the same manner as in Example 1, and the same evaluation was performed. As a result, similar to Example 1, spots, roughening, and layer peeling were improved. Good effects were obtained.

<Example 7> In Example 1, the NO gas cylinder was changed to a SiF ₄ gas cylinder, and a PH ₃ / H ₂ gas was further used in an upper layer from a cylinder (not shown). 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 layer peeling was obtained.

Example 8 In the lower layer, Mg (C ₅ H ₅ ) ₂ / He gas was used from a closed container (not shown), and PH ₃ /
An H ₂ gas and an N ₂ gas were further used, and a light receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 9, and the same evaluation was performed. In addition, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 9> In the lower layer, CH ₄ gas and B ₂ H ₆ / H ₂ gas were further used, and in the upper layer, the CH ₄ gas cylinder was filled with C ₂ H ₂ gas (purity 9).
(9.9999%) Instead of a cylinder, an electrophotographic light-receiving member was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 10,
As a result of a similar evaluation, a favorable effect of improving spotting, roughening, and layer peeling was obtained as in Example 1.

Using _{Mg (C 5 H 5) 2} / He gas from the closed vessel <Example 10> (not shown), B ₂ H ₆
The gas cylinder was changed to a PH ₃ / H ₂ gas cylinder, a SiF ₄ gas was further used from a cylinder (not shown), and a light receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 11, and the same. As a result of the evaluation, as in the case of Example 1, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 11> In Example 1, the CH ₄ gas cylinder was replaced with NH ₃ gas (purity 9).
9.999%) Instead of a cylinder, an NH ₃ gas was used in the upper layer, and 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. In the same manner as in Example 1, a good effect of improving the popping, roughening, and layer peeling was obtained.

<Example 12> CH ₄ gas was used in the lower layer, and Si
Further using F ₄ gas, according to the preparation conditions shown in Table 13,
A light-receiving member for electrophotography was prepared in the same manner as in Example 6, and the same evaluation was carried out. As a result, similar effects to those in Example 6 were obtained.

<Example 13> CH ₄ gas was changed to C ₂ H ₂ gas in the lower layer, PH ₃ / H ₂ gas was used from a cylinder (not shown), and Si ₂ H ₆ gas (purity) was used from the cylinder (not shown) in the upper layer. 99.99%) and Si ₂ F ₆ gas (purity 99.99%) were further used, and a light receiving member for electrophotography was prepared in the same manner as in Example 9 under the preparation conditions shown in Table 14, and the same evaluation was performed. However, as in the case of Example 9, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 14> A light receiving member for electrophotography was prepared in the same manner as in Example 1 by further using Si ₂ F ₆ gas, PH ₃ gas, and NH ₃ gas from a cylinder (not shown) under the production conditions shown in Table 15. It was made and evaluated in the same manner. As in Example 1, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 15> Under the 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. A good effect of improving peeling was obtained.

<Example 16> In Example 1, the outer diameter of the cylindrical aluminum-based support was set to 80 mm, and a light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 17; The same evaluation as in Example 1 was 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, CH ₄ gas was changed to C ₂ H ₂ gas, the temperature of the cylindrical aluminum-based support was set to 500 ° C, and the upper layer was made of poly-Si under the conditions shown in Table 21. An electrophotographic light-receiving member composed of (H, X) was prepared in the same manner as in Example 9 and evaluated in the same manner. Effect was obtained.

Example 23 The electrophotographic light-receiving member of the present invention was formed 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 a GeH ₄ 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
1,1042,1044,1045,1046,1047,1048 and auxiliary valve 101
8 gradually open, SiH ₄ gas, H ₂ gas, SiF ₄ gas, B ₂ H ₆ / H
_Two gases, NO gas, AlCl ₃ / He gas, and Cu (C ₄ H ₇ N ₂ O ₂ ) ₂ / He gas were flowed into the plasma generation region 1109 through gas discharge holes (not shown) of the gas introduction pipe 1110. At this time, SiH ₄ gas flow rate 15
0 SCCM, H ₂ gas flow rate is 20 SCCM, SiF ₄ gas flow rate 10 SCCM, NO
Gas flow rate is 10 SCCM, B ₂ H ₆ / H ₂ gas flow rate is 100 for SiH ₄
The gas flow rate of AlCl ₃ / He is 400 SCCM, Cu (C ₄ H ₇
N ₂ O ₂ ) ₂ / He each mass flow controller 1021,1022,1024,1025,1026,1027,1028 so that the gas flow rate is 10 SCCM
Was adjusted. 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 the μW power supply (not shown) is reduced to 0.
Setting to 5 W / cm ³ , μW power is introduced into the plasma generation region 1109 through the waveguide 1103 and the dielectric window 1102 to generate μW glow discharge, and a lower layer is formed on the cylindrical aluminum-based support 1107. Started. During the formation of the lower layer, the SiH ₄ gas flow rate was 150 SCCM, the SiF ₄ gas flow rate was 10 SCCM, the B ₂ H ₆ / H ₂ gas flow rate was 100 ppm with respect to SiH ₄ , the NO gas flow rate was 10 SCCM, Cu (C
_{4 H 7 N 2 O 2)} 2 / He gas flow rate to be constant flow rate of 10 SCCM, as H ₂ gas flow rate increases at a constant rate 500SCCM from 20SCCM, AlCl ₃ / He gas flow rate support side At 0.01 μm, it decreases from 400 SCCM to 80 SCCM at a constant rate.
At the upper layer side of 0.01 μm, the mass flow controllers 1021, 1022, 10
24, 1025, 1026, 1027, 1028 were adjusted, the μW glow discharge was stopped when the lower layer having a layer thickness of 0.02 μm was formed, and the outflow valves 1041, 1042, 1044, 1045, 1046, 1047, 1048 and the auxiliary valve By closing 1018, the flow of gas into the plasma generation region 1109 was stopped, 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, 1044, 1045, 1046 and the auxiliary valve 1018 are gradually opened to open the SiH ₄ gas, H ₂ gas, SiF ₄ gas, B ₂ H ₆ / H ₂ gas and NO gas were introduced into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, Si
H ₄ gas flow rate 500 SCCM, H ₂ gas flow rate _{300SCCM, B 2 H 6 / H} 2
Gas flow rate is 1000ppm with respect to SiH ₄ gas, SiF ₄ gas flow rate is 2
The mass flow controllers 1021, 1022, 1024, 1025, and 1026 adjusted the flow rates of 0 SCCM and NO gas to 13 SCCM. The pressure in the deposition chamber 1101 was adjusted to be 0.4 mTorr. Thereafter, the power of a μW power supply (not shown) was set to 0.5 W / cm ³ to generate a μW glow discharge in the plasma generation chamber 1109 similarly to the lower layer, and the first layer region of the upper layer was formed on the lower layer. The formation was started, and a first layer region of an upper layer having a layer thickness of 1 μm was formed.

Next, in order to form the second layer region of the upper layer, the outflow valves 1041, 1042, 1044 and the auxiliary valve 1018 are gradually opened, and SiH ₄ gas, H ₂ gas, and SiF ₄ are connected to the gas introduction pipe 1110. The gas was allowed to flow into the plasma generation space 1109 through the illustrated gas discharge holes. At this time, the SiH ₄ gas flow rate was 700 SCCM, and the H ₂ gas flow rate was 500
SCCM, SiF ₄ gas flow rate was adjusted with mass flow controllers 1021,1022,1024 each so that 30 SCCM. Deposition chamber
The pressure in 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 , and a μW glow discharge was generated in the plasma generation chamber 1109 in the same manner as 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, 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 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 mass flow controllers 1021 and 1023 adjusted the flow rates of the SiH ₄ gas to 150 SCCM and the flow rate of the CH ₄ gas to 500 SCCM. The pressure in the deposition chamber 1101 was 0.3 mTorr. Thereafter, the power of a μW power supply (not shown) 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.

The lower layer of the electrophotographic light-receiving member of Example 23 was 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.

Changing the CH ₄ gas cylinder <Example 24> Example 1 to C ₂ H ₂ gas cylinder, the generating conditions shown in Table 23, 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 25> In Example 1, the B ₂ H ₆ / H ₂ gas cylinder was changed to a PF ₃ / H ₂ gas cylinder, CH ₄ gas was further used in the lower layer, and SiF ₄ gas was used in all layers. Under the conditions shown in Table 24, a light-receiving member for electrophotography was prepared in the same manner as in Example 1, and the same evaluation was carried out. As in Example 1, spots, roughness, and layer peeling were improved. Good effects were obtained.

Changing the NH ₃ gas cylinder a CH ₄ gas cylinder <Example 26> Example 1, using SnH ₄ gas from a cylinder (not shown), using _{Mg (C 5 H 5) 2} / He gas from the sealed container (not shown) Then, under the conditions shown in Table 25, a light receiving member for electrophotography was prepared in the same manner as in Example 1, and the same evaluation was carried out. An improved good effect was obtained.

<Example 27> The B ₂ H ₆ / H ₂ gas cylinder was changed to a PF ₃ / H ₂ gas cylinder,
Using F ₄ gas and under the conditions shown in Table 26, an electrophotographic light-receiving member was prepared in the same manner as in Example 6, and the same evaluation was performed. A good effect of improving the peeling of the layer was obtained.

<Example 28> A light receiving member for electrophotography was used in the same manner as in Example 1 by changing the CH ₄ gas cylinder to a C ₂ H ₂ gas cylinder, further using Si ₂ H ₆ gas in the upper layer, and producing conditions shown in Table 27. Was prepared and evaluated in the same manner. As in Example 1, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 29> In Example 1, the CH ₄ gas cylinder was changed to an NH ₃ gas cylinder, and a PH ₃ / H ₂ gas was further used in an upper layer from a cylinder (not shown). 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 layer peeling was obtained.

<Example 30> In Example 1, NO gas and B ₂ H ₆ / H ₂ were further added to the lower layer.
_{Gas, Mg (C 5 H 5)} 2 / He gas, instead of the H ₂ gas using He gas (not shown) to the upper layer, the generating conditions shown in Table 29, for similarly electrophotographic Example 1 A light-receiving member was prepared and evaluated in the same manner. As in Example 1, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 31> In all layers, SiH ₄ gas, H ₂ gas, SiF ₄ gas, CH ₄ gas, B ₂ H ₆ / H ₂ gas, NO gas, AlCl ₃ / He gas, Cu (C ₄ H ₇ N ₂ O ₂ ) ₂
/ He gas is supplied from the cylinder (not shown) in the upper layer to PH ₃ / H
_{Using two} gases, a light receiving member for electrophotography was prepared in the same manner as in Example 1 under the conditions shown in Table 30, and the same evaluation was carried out. A good effect of improving peeling was obtained.

<Example 32> Under the conditions shown in Table 31, a light receiving member for electrophotography was prepared in the same manner as in Example 31, and the same evaluation was carried out. A good effect was obtained which was improved with respect to.

<Example 33> further using C ₂ H ₂ gas in the upper layer, the generating conditions shown in Table 32, to create the electrophotographic light-receiving member as in Example 1, was subjected to the same evaluation In the same manner as in Example 1, a good effect of improving the popping, roughening, and layer peeling was obtained.

<Example 34> In Example 1, the CH ₄ gas cylinder was changed to a C ₂ H ₂ gas cylinder, and the B ₂ H ₆ / H ₂ gas cylinder was changed to a PH ₃ / H ₂ gas cylinder. 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 layer peeling was obtained.

<Example 35> An H ₂ S gas (purity: 99.999%) was further used from a cylinder (not shown), and a light receiving member for electrophotography was prepared in the same manner as in Example 31 under the preparation conditions shown in Table 34. As a result of good evaluation, as in Example 31, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

Further using C ₂ H ₂ gas from a cylinder of <Example 36> (not shown), by creating the conditions shown in 35 Table similarly to create a light-receiving member for electrophotography in Example 31, subjected to the same evaluation The example
As in the case of 31, good effects were obtained which were improved against spotting, roughening, and layer peeling.

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

<Example 38> further using from _{Mg (C 5 H 5) 2} / He gas sealed container (not shown), the generating conditions shown in Table 37, creating an electrophotographic light receiving member as in Example 36 And the same evaluation was performed,
As in the case of Example 36, a good effect of improving spotting, roughening, and layer peeling was obtained.

<Example 39> Under the conditions shown in Table 38, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was performed. A good effect was obtained which was improved with respect to.

<Example 40> Under the conditions shown in Table 39, a light-receiving member for electrophotography was prepared in the same manner as in Example 38, and the same evaluation was carried out. A good effect was obtained which was improved with respect to.

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

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

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

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

<Example 45> A light receiving member for electrophotography was produced in the same manner as in Example 36 under the production conditions shown in Table 44 by further using H ₂ S gas from a cylinder (not shown), and the same evaluation was performed. However, the embodiment
As in the case of 36, a good effect was obtained which was improved with respect to spotting, roughening, and layer peeling.

<Example 46> Under the conditions shown in Table 45, a light receiving member for electrophotography was prepared in the same manner as in Example 36, and the same evaluation was carried out. A good effect was obtained which was improved with respect to.

<Example 47> A light receiving member for electrophotography was produced in the same manner as in Example 36 under the production conditions shown in Table 46 by further using H ₂ S gas from a cylinder (not shown), and the same evaluation was performed. However, the embodiment
As in the case of 36, a good effect was obtained which was improved with respect to spotting, roughening, and layer peeling.

<Example 48> Under the conditions shown in Table 47, a light-receiving member for electrophotography was prepared in the same manner as in Example 36, and the same evaluation was performed. As in Example 36, spots, roughening, and layer peeling were observed. A good effect was obtained which was improved with respect to.

<Example 49> Under the conditions shown in Table 48, a light-receiving member for electrophotography was prepared in the same manner as in Example 38, and the same evaluation was carried out. A good effect was obtained which was improved with respect to.

<Example 50> A light-receiving member for electrophotography was produced in the same manner as in Example 36 under the production conditions shown in Table 49, further using NH ₃ gas and H ₂ S gas, and the same evaluation was performed. In the same manner as in Example 36, a favorable effect of improving spotting, roughening, and layer peeling was obtained.

<Example 51> Under the conditions shown in Table 50, an electrophotographic light-receiving member was prepared in the same manner as in Example 36, and the same evaluation was carried out. A good effect was obtained which was improved with respect to.

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

<Example 53> Under the conditions shown in Table 52, a light-receiving member for electrophotography was prepared in the same manner as in Example 38, and the same evaluation was carried out. A good effect was obtained which was improved with respect to.

<Example _{54> Mg (C 5 H 5} ) further using ₂ / He gas, the generating conditions shown in 53 Table creates an electrophotographic light-receiving member as in Example 38, the same evaluation As a result, similar effects as in Example 38 were obtained, and a favorable effect of improving spotting, roughening, and layer peeling was obtained.

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

<Example 56> Under the conditions shown in Table 55, a light-receiving member for electrophotography was prepared in the same manner as in Example 1, and the same evaluation was carried out. As in Example 1, spots, roughening, and layer peeling were observed. A good effect was obtained which was improved with respect to.

Example 57 The lower layer of the electrophotographic light-receiving member of the present invention was formed by an RF sputtering method, and the upper layer was formed by an RF glow discharge decomposition method.

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

In the figure, 1405 is Si, Al, which is a raw material for forming the lower layer.
The target is made of Cu, 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.

The lower layer is formed by gradually opening the outflow valves 1420, 1421 and 1422 and the auxiliary valve 1432 to form the SiH ₄ gas, H ₂ gas,
r Gas was allowed to flow into the deposition chamber 1401. At this time, the SiH ₄ gas flow rate was 30 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 30 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, forming a lower layer with a layer thickness of 0.05 μm. When the RF glow discharge is stopped, the outflow valves 1420, 1421, 1423 and the auxiliary valve 1432 are closed, and the flow rate of gas into the deposition chamber 1401 is stopped.
The formation of the lower layer has been 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, the upper layer is formed by a glow discharge decomposition method using the apparatus shown in FIG. Under the conditions shown in Table 56, an electrophotographic light-receiving member was prepared in the same manner as in Example 1, and the same evaluation was carried out. As in Example 1, it was improved against spotting, roughening, and layer peeling. A good effect was obtained.

Further, the lower layer of the electrophotographic light-receiving member of Example 57 was
Analysis by MS revealed that the contents of silicon atoms, hydrogen atoms, and aluminum atoms in the thickness direction changed as desired.

[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, halftones are clearly produced, and high-quality images 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 containing copper atoms (Cu) in the lower layer, the injection property and adhesion of electric charges (photocarriers) between the aluminum-based support and the upper layer are improved. Since the traveling property of the electric charge (photocarrier) in the lower layer is remarkably improved, there is a feature that a remarkable improvement is observed in image characteristics and durability.

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

[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. FIGS. 3 to 8 show aluminum atoms (Al), copper atoms (Cu), magnesium atoms (Mg), and germanium atoms (Ge) contained in the lower layer, respectively.
FIG. 4 is an explanatory diagram of distribution states of tin atoms (Sn), halogen atoms (X _C ), atoms for adjusting durability (CNOc), and atoms for adjusting image quality (M _C ). 9 to 16 show silicon atoms (Si), hydrogen atoms (H), copper atoms (Cu), magnesium atoms (Mg), and germanium atoms (Ge) contained in the lower layer, respectively. FIG. 3 is an explanatory diagram of distribution states of tin atoms (Sn), halogen atoms (X _C ), atoms for adjusting durability (CNO _c ), and atoms for adjusting image quality (M _C ). FIGS. 17 to 36 show the conductivity controlling atoms (M), carbon atoms (C) and / or nitrogen atoms (N) and / or oxygen atoms (O), and germanium atoms contained in the upper layer, respectively. FIG. 37 is an explanatory view of a distribution state of (Ge) and / or tin atoms (Sn), magnesium atoms (Mg), and copper atoms (Cu). FIG. 37 shows a light receiving layer of the electrophotographic light receiving member of the present invention. FIG. 38 is a schematic diagram of a manufacturing apparatus by a glow discharge method using RF, which is an example of an apparatus for forming a light-receiving member for electrophotography according to the present invention. FIG. 39 is an enlarged view of the cross section of the support when the surface of the aluminum-based support is subjected to so-called dimple processing when forming the electrophotographic light-receiving member of the present invention. FIG. 40 is a light receiving member for electrophotography of the present invention. FIG. 41 is a schematic explanatory view of a deposition apparatus when a microwave glow discharge method is used to form a light receiving layer. FIG. 41 is an illustration of an apparatus for forming a light receiving layer of an electrophotographic light receiving member of the present invention. FIG. 42 is a schematic explanatory view of a manufacturing apparatus by a glow discharge method using microwaves as an example. FIG. 42 is an example of an apparatus for forming a light receiving layer of an electrophotographic light receiving member of the present invention, which is manufactured by an RF sputtering method. FIG. 2 is a schematic explanatory view of the device. 1. With reference to FIG. 1, 100... The electrophotographic light receiving member 101 of the present invention 101... An aluminum-based support 102... A light receiving layer 103... A lower layer 104. 200: Conventional light receiving member for electrophotography 201: Aluminum support 202: Photosensitive layer made of A-Si 203: Free surface In FIG. 37, 1000: Deposition device by RF glow discharge decomposition method 1001 … Deposition chamber 1005… Cylindrical aluminum support 1008… Gas introduction pipe 1009… Gas discharge hole 1012… High frequency matching box 1014… Heater 1015… Leak valve 1016… Main valve 1017… Vacuum gauge 1018 Auxiliary valve 1020 Source gas supply device 1021-1027 Mass flow controller 1031-1037 Gas inflow valve 1041-1047 Gas outflow valve 1051-1057 Valve of source gas cylinder 1061-1067 …pressure Integrators 1071 to 1077: Raw material gas cylinder 1078: Closed container for raw material In FIGS. 40 and 41, 1100: Deposition device 1101 by microwave glow discharge method 1101: Deposition chamber 1102 Dielectric window 1103 Waveguide portion 1107 Cylindrical aluminum support 1109 Plasma generation region 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 to 1418… Gas inflow valve 1420 to 1422… Gas outflow valve 1432… Auxiliary valve 1433… High frequency matching box 1435… Vacuum gauge 1500 …… Source gas supply device 1501 …… Deposition device by RF sputtering

Continuing on the front page (72) Inventor Toshimitsu Kariya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Hiroaki Shinno 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-58-111046 (JP, A) JP-A-62-15554 (JP, A) JP-A-59-212845 (JP, A)

Claims (1)

(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. A lower layer composed of an inorganic material containing atoms, silicon atoms, hydrogen atoms, and copper atoms, and having a portion containing the aluminum atoms, silicon atoms, and hydrogen atoms in a non-uniform distribution in a layer thickness direction; And a non-monocrystalline material containing at least one of a hydrogen atom and a halogen atom, and at least one of a carbon atom, a nitrogen atom, and an oxygen atom in a layer region in contact with the lower layer. A light receiving member comprising an upper layer containing two atoms.