JP2620796B2 - Light receiving member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field to which the Invention Pertains] The present invention relates to an electromagnetic wave such as light (here, light in a broad sense, meaning ultraviolet light, visible light, infrared light, X-ray, γ-ray, etc.). To a light receiving member that is sensitive to light.

[Description of conventional technology and its problems]

In the field of image formation, the photoconductive material constituting the light receiving layer of the light receiving member has high sensitivity, a high SN ratio [photocurrent (Ip) / dark current (Id)], and spectral characteristics of the electromagnetic wave to be irradiated. In addition to being required to have an absorption spectrum characteristic adapted to the above, to have a quick photoresponse, to have a desired dark resistance value, etc., it is required to be harmless to the 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, it is important that the member is non-polluting when used.

In view of the above requirements, amorphous silicon (hereinafter referred to as A-Si) has been used as a photoconductive material, and has been applied as a light receiving member for electrophotography.

FIG. 2 is a cross-sectional view schematically illustrating the layer structure of such a conventional electrophotographic light-receiving member, wherein 201 is an aluminum-based support, and 202 is a light-receiving layer made of A-Si. Show. Such an electrophotographic light-receiving member is generally formed by heating an aluminum-based support 201 to 50 ° C. to 350 ° C. and forming a film on the support by vapor deposition, thermal CVD, plasma CVD, or sputtering. Light-receiving layer composed of A-Si
202 is created.

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 is a problem. In order to solve these problems, an electrophotographic photosensitive member comprising an intermediate layer containing at least aluminum and an A-Si photosensitive layer on an aluminum-based support has been proposed as disclosed in JP-A-59-28162. In this proposal, the intermediate layer containing at least aluminum relaxes the stress generated due to the difference in the thermal expansion coefficient between the aluminum-based support and the A-Si photosensitive layer, so that cracks and films in the A-Si photosensitive layer are reduced. The peeling is reduced.

However, there is still a problem that needs to be solved as described below even by the proposal of Japanese Patent Application Laid-Open No. 59-28162.

That is, according to the method described in this publication, an intermediate layer containing aluminum atoms (Al) and silicon atoms (Si) is formed on an aluminum-based support, and then a photosensitive layer made of A-Si is formed. Although the electrophotographic photoreceptor has a certain improvement in the problem of cracks and film peeling as compared with other electrophotographic photoreceptors not having the above-mentioned intermediate layer, when used continuously for a long time, Crack,
A problem such as peeling occurs.

By the way, the above-mentioned intermediate layer is formed by a glow discharge decomposition method using AlCl ₃ , Al (CH ₃ ) ₃ , SiH ₄ or the like as a raw material gas to form aluminum atoms (Al) and silicon atoms (Si) as desired. The process is performed by adjusting the flow rate of the source gas so as to be distributed in the layer.In the intermediate layer thus formed, Al and Si change according to the flow rate of the source gas. However, hydrogen atoms (H) and halogen atoms (X) are distributed throughout the layer. In the intermediate layer, there is a region on the support body side where the number of silicon atoms (Si) is small, and the region contains a large number of hydrogen atoms (H) and halogen atoms (X). Furthermore, in the region of the intermediate layer mainly composed of aluminum atoms (Al),
These hydrogen atoms (H) and halogen atoms (X) are locally aggregated. Due to these reasons, in the electrophotographic photoreceptor proposed by the above-mentioned publication, when it is used continuously for a long time, the structure of the light receiving layer is relaxed, which causes cracks and film peeling. Become.

In addition, regarding electrophotographic light-receiving members having a light-receiving layer composed of A-Si, electrical, optical, 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,
There are areas that need to be further improved in order to improve overall 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. It is necessary to prevent the occurrence of problems such as the occurrence of image defects due to the applied mechanical pressure of the impact for a relatively short period of time and the peeling of the A-Si film, thereby impairing the durability of the electrophotographic light-receiving member. .

Further, it is necessary to solve the problem that cracks and peeling occur in the A-Si film due to the stress generated due to the difference in the coefficient of thermal expansion between the aluminum-based support and the A-Si film, thereby reducing the yield in productivity. There is.

Therefore, while the characteristics of the A-Si material itself are improved, the above-mentioned problems are solved and the above-mentioned requirements are satisfied when designing the electrophotographic light-receiving member. It is necessary to make improvements from a comprehensive point of view.

[Object of the invention]

The present invention provides a light-receiving member which solves the above-mentioned conventional problems and satisfies the above-mentioned various requirements by using an aluminum-based material as a support, and is particularly suitable as an electrophotographic photoreceptor. The main purpose is to do so.

Another object of the present invention is to provide a high-quality image having a desired mechanical durability without any problems such as cracks in the light-receiving layer and film peeling even when used continuously for a long time, and constantly stably. An object of the present invention is to provide an electrophotographic photoconductor using an aluminum-based material as a support.

[Structure and effect of the invention]

The present invention overcomes the above-mentioned various problems and satisfies the above-mentioned various needs and achieves the above-mentioned objects, and is provided by the present invention, and is particularly a light-receiving member suitable as an electrophotographic photoreceptor. The outline is as follows.

That is, in a light-receiving member having an aluminum-based support and a light-receiving layer having a multilayer structure having at least photoconductivity on the support, the light-receiving layer is arranged such that at least aluminum atoms (Al ), An inorganic material containing a silicon atom (Si), a hydrogen atom (H) and / or a halogen atom (X), and containing at least one of an alkali metal atom, an alkaline earth metal layer, and a transition metal atom. And the aluminum atoms decrease upward from the aluminum-based support, silicon atoms, hydrogen atoms, and halogen atoms (X) both increase upward from the support, and A lower layer having a content of 20% or more in the vicinity of the upper part, and a silicon atom as a base, and a hydrogen atom and a halogen atom (X). Also characterized in that it consists constituted the top layer in a non-monocrystalline material containing either. Note that the non-single-crystal material includes and means an amorphous material (including a so-called microcrystalline material) and a polycrystalline material (hereinafter, referred to as “Non-Si (H, X)”).

The light receiving member of the present invention having the above-mentioned layer structure, which is optimal for electrophotography, solves the above-mentioned problems and satisfies the above-mentioned various requirements, and has extremely excellent electrical properties, optical properties, and photoconductive properties. It shows characteristics, image characteristics, durability, stability and use environment characteristics.

In addition, the light receiving member of the present invention particularly has a lower layer in which the number of aluminum atoms (Al) is increased on the support side and the number of silicon atoms (Si), hydrogen atoms (H) and halogen atoms (X) are reduced. In the upper region of the lower layer, aluminum atoms (Al) are reduced and silicon atoms (Si) and hydrogen atoms (H) and / or halogen atoms (X) are distributed so as to be increased. This can prevent structural relaxation due to agglomeration of hydrogen atoms and halogen atoms, which are often contained on the support side of the lower layer, which has been a problem in the long-term use, and the cracks and peeling of the deposited film provided for it can be prevented. Can be prevented.

In addition, the lower layer contains aluminum atoms (Al), silicon atoms (Si), and particularly hydrogen atoms (H) in a non-uniform distribution state in the layer thickness direction, so that the aluminum-based support and the upper layer can be separated. Injectability of charges (photocarriers) between layers is improved, and furthermore, the systematic structural continuity of constituent elements between the aluminum-based support and the upper layer is improved, so that image characteristics such as roughness and spots are improved. It is possible to stably and repeatedly obtain a high-quality image with improved halftone sharpness and high resolution.

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-S
Cracks and peeling of the i (H, X) film can be prevented, and the yield in productivity can be improved.

In particular, in the present invention, by containing at least one of alkali metal atoms, alkaline earth metal atoms, and transition metal atoms in the lower layer, hydrogen atoms and halogen atoms contained in the lower layer are unknown, although details are unknown. It can be contained in a more dispersed manner, and the temporal relaxation of the structure of the lower layer can be further reduced. As a result, even when used for a long time, cracks and film peeling can be suppressed. One of the distinguishing features of the lower layer containing the metal atoms is that the charge (photocarrier) between the aluminum-based support and the upper layer is different.
Significant improvement in image characteristics and durability due to significant improvement in the injection and adhesion properties of GaN and the mobility of charges (photocarriers) in the lower layer, resulting in improved production stability and quality stability I do.

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

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

An electrophotographic light-receiving member 100 shown in FIG. 1 has an aluminum-based support 101 for an electrophotographic light-receiving member on which aluminum atoms (Al), silicon atoms (Si), and hydrogen atoms (H) are formed. , A lower layer 103 containing a non-uniform distribution in a layer thickness direction, and an upper layer 104 made of Non-Si (H, X).
And a light receiving layer 102 having a layer configuration of 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 pure aluminum include, for example, JIS1100, Si and Fe: 1.0% by weight or less, Cu: 0.05 to 0.20% by weight, Mn: 0.05% by weight or less, Zn: 0.10% by weight or less, 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%, M
n: 0.40 to 1.0 wt%, Mg: 0.40 to 0.8 wt%, Zn: 0.25 wt% or less, Cr: 0.10 wt% or less, Al: balance.

As an Al-Mn system, for example, JIS3003, Si: 0.6% by weight
Hereinafter, Fe: 0.7% by weight or less, Cu: 0.05 to 0.20% by weight, Mn: 1.
0 to 1.5% by weight, Zn: 0.10% by weight or less, Al: balance.

As an Al-Si system, for example, JIS4032, Si: 11.0 to 13.5
Wt%, Fe: 1.0 wt% or less, Cu: 0.50-1.3 wt%, Mg:
0.8 to 1.3 wt%, Zn: 0.25 wt% or less, Cr: 0.10 wt% or less, Ni: 0.5 to 1.3 wt%, Al: balance.

As an Al-Mg type, for example, JIS5086, Si: 0.40% by weight
Below, Fe: 0.50% by weight or less, Cu: 0.10% by weight or less, Mn: 0.2
0 to 0.7 wt%, Mg: 3.5 to 4.5 wt%, Zn: 0.25 wt% or less, Cr: 0.05 to 0.25 wt%, Ti: 0.15 wt% or less, Al: balance.

Further, Si: 0.50% by weight or less, Fe: 0.25% by weight or less,
Cu: 0.04 to 0.20% by weight, Mn: 0.01 to 1.0% by weight, Mg: 0.5 to 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%, H _2: Al100 grams 1.0cc or less with respect to, Al: include balance.

Further, further, Si: 0.12% by weight or less, Fe: 0.15% by weight
Below, Mn: 0.30% by weight or less, Mg: 0.5 to 5.5% by weight, Zn: 0.0
1 to 1.0 wt%, Cr: 0.20 wt% or less, Zr: 0.01 to 0.25 wt%, Al: balance.

As an Al-Mg-Si system, for example, JIS6063, Si: 0.20 to
0.6% by weight, Fe: 0.35% by weight or less, Cu: 0.10% by weight 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 system 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, M:
n: 0.20 to 0.7% by weight, Mg: 1.0 to 2.0% by weight, Zn: 4.0 to 5.0
Wt%, Cr: 0.30 wt% or less, Ti: 0.20 wt% or less, Zr:
0.25% by weight or less, V: 0.10% by weight or less, Al: balance.

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 machinability 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 surface or an uneven surface, and its thickness is appropriately determined so that a desired electrophotographic light-receiving member can be formed.
When flexibility as an electrophotographic light-receiving member is required, it can be made as thin as possible within a range in which the function as a support is sufficiently exhibited. However, in view of the production and handling of the support and the mechanical strength, it is usually 10
μm or more.

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

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

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

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

The irregularities due to the plurality of spherical trace 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 light receiving member of the present invention contains at least an aluminum atom, a silicon atom, a hydrogen atom and / or a halogen atom as a constituent element, and further includes an alkali metal atom, an alkaline earth metal atom, and a transition metal atom. Wherein the aluminum atoms decrease from the aluminum-based support toward the top, and the silicon atoms and the hydrogen atoms and / or the halogen atoms both increase from the support toward the top. And the content of the aluminum atoms increases near the upper portion.
It is configured to be at least 20 atomic%.

Then, the aluminum atoms (A
l), silicon atoms (Si), hydrogen atoms (H), and / or halogen atoms (X) are uniformly contained in the entire layer region of the lower layer, but the distribution concentration in the layer thickness direction is It 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.

The lower layer in the light receiving member of the present invention may contain germanium atoms and / or tin atoms (Sn) as needed. The lower layer may also contain one or more selected from carbon atoms (C), nitrogen atoms (N) and oxygen atoms (O), if necessary. Furthermore, the lower layer may contain atoms (Dopants) for controlling the conductivity (M) and / or atoms (Mc) for adjusting the image quality, if necessary.

In the lower layer of the light receiving member of the present invention, the above-described metal atoms and halogen atoms (X), and further, the atoms contained as necessary, are all uniformly distributed over the entire lower layer. It may be contained in a distributed state, or may be contained evenly in the entire layer region of the lower layer, but may be contained in a state of being distributed unevenly in the layer thickness direction. good. 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)
And / or halogen atoms (X) are continuously and evenly distributed, 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) are distributed. ), The distribution concentration of hydrogen atoms (H) and halogen atoms (X) in the layer thickness direction increases from the support side toward the upper layer, so that the aluminum-based support, the lower layer and the lower layer Excellent affinity with the upper layer.

In this case, it is desirable to form the layer so that the content of aluminum atoms contained in the lower layer on the side of the support can be in a distribution state of 50 atomic% or more.

When the content of aluminum atoms contained on the support side of the lower layer is less than 50 atomic%, hydrogen atoms (H) and halogen atoms (X) are localized near the interface between the support and the lower layer, and The affinity with the layer decreases.

Further, the content of aluminum atoms in the region near the interface between the lower layer and the upper layer is desirably 20 atomic% or more.

This is because if the content of aluminum atoms contained in the region is less than 20 atomic%, the metallic properties of the lower layer are weakened, and an electric barrier is formed between the lower layer and the upper layer.

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, but is preferably 5 to 80 atomic%. More preferably, the content is 10 to 75 atomic%, and most preferably, 20 to 70 atomic%.

In the present invention, the content of the hydrogen atoms (H) and / or the halogen atoms (X) contained in the lower layer is closely related to the silicon atoms contained in the lower layer, and Desirably, the content is 0.01 to 100 atomic%, more preferably 0.1 to 70 atomic%, and most preferably 1 to 50 atomic%.

By containing the above amount of hydrogen atoms with respect to silicon atoms, the structural flexibility of the lower layer is increased, the structure is sufficiently relaxed in a short time when the lower layer is formed, and the electrophotographic characteristics for a long time are affected. It is possible to prevent the structure from being relaxed.

In the present invention, an alkali metal contained in the lower layer,
As an alkaline earth metal and a transition metal, a sodium atom (Na) and / or a yttrium atom (Y) and / or
Or a manganese atom (Mn) and / or a zinc atom (Z
n) and / or a copper atom (Cu) and / or a magnesium atom (Mg) or the like, whereby the hydrogen atom (H) and the halogen atom (X) contained in the lower layer can be more dispersed, Aggregation of hydrogen, which is considered to be the cause of cracks and peeling, can be prevented.

Further, the effect of improving the charge injection property between the aluminum-based support and the upper layer and / or the effect of improving the charge transportability in the lower layer and / or the effect of improving the charge transfer property between the aluminum-based support and the upper layer. The effect of improving the adhesion can be obtained.

As the content of the metal contained in the lower layer,
It is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 2 × 10 ⁵ atomic ppm, more preferably 1 × 10 ² to 1 × 10 ⁵ atomic ppm, and most preferably ⁵ × 10 ⁵ atomic ppm. × 1
It is desirably in the range of 0 ^{2 to} 5 × 10 ⁴ atomic ppm.

The lower layer contains germanium atoms (Ge) and / or tin atoms (Sn) as necessary, thereby improving the charge injection property between the aluminum-based support and the upper layer, and / or the lower layer. And / or an effect of improving the adhesion between the aluminum-based support and the upper layer. 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. 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 (Cl), a bromine atom (Br), and an iodine atom (I) are used. In the present invention, the lower layer mainly contains a fluorine atom (F) and / or a chlorine atom (Cl) and / or a bromine atom (Br) and / or an iodine atom (I) as a halogen atom (X). The dangling bonds such as silicon atoms (Si) and aluminum atoms (Al) contained in the lower layer are compensated for, and the systematic structure is stabilized to improve the layer quality.

Carbon atoms (C) as atoms for adjusting durability in the lower layer
And / or containing a nitrogen atom (N) and / or an oxygen atom (O) to improve the charge injection property mainly between the aluminum-based support and the upper layer, and / or The effect of improving the charge transportability and / or the effect of improving the adhesion between the aluminum-based support and the upper layer can be obtained. Further, the effect of controlling the forbidden band width can be obtained in a layer region where the content of aluminum atoms (Al) is small in the lower layer. The atoms that adjust the durability contained in the lower layer (CN
The content of Oc) is preferably 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 (Mc) for adjusting the image quality contained as necessary include atoms belonging to Group III of the periodic table excluding aluminum atoms (Al) (hereinafter abbreviated as “Group III atoms”), nitrogen Atoms belonging to Group V of the Periodic Table excluding the atoms (N) (hereinafter abbreviated as “Group V atoms”), oxygen atoms (O)
Atoms belonging to Group VI of the Periodic Table (excluding "Group VI atoms")
(Abbreviated as). Specific examples of Group III atoms include B (boron), Ga (gallium), In (indium), and Tl (thallium), with B and Ga being particularly preferred. As the group V atom, specifically, P (phosphorus), As
(Arsenic), Sb (antimony), Bi (bismuth) and the like, and P and As are particularly preferable. Specific examples of Group VI atoms include S (sulfur), Se (selenium), Te (tellurium), Po
(Polonium) and the like, and S and Se are particularly preferable. In the present invention, the lower layer contains a Group III atom, a Group V atom or a Group VI atom as an atom (Mc) for adjusting the image quality, so that the electric charge mainly between the aluminum-based support and the upper layer is increased. And / or the effect of improving the mobility of charges 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 (Mc) for adjusting the image quality contained in the lower layer is preferably 1 × 10 ^{−3 to} 5 × 10 ⁴ atomic ppm, more preferably 1 × 10 ⁻² to 1 × 10 ⁴ atomic ppm, Optimally 1 ×
It is desirable that the concentration be 10 ^{-1 to} 5 × 10 ³ atomic ppm.

In the present invention, the lower layer is formed, for example, by the same vacuum deposition film forming method as that for the upper layer described later, with the numerical conditions of the film forming parameters appropriately set so as to obtain desired characteristics. Specifically, for example, a glow discharge method (AC discharge C such as low-frequency CVD, high-frequency CVD or microwave CVD) is used.
VD or DC discharge CVD etc.), ECR-CVD method, sputtering method, vacuum deposition method, ion plating method, optical CV
Method D, an active species (A) generated by decomposing a raw material gas, and an active species (B) generated from a film-forming chemical substance that chemically interacts with the active species (A). And
A method of forming a material by separately introducing them into a film forming space for forming a deposited film and chemically reacting them to form a material (hereinafter abbreviated as “HRCVD method”), a material gas of the material, A method in which a halogen-based oxidizing gas having a property of oxidizing is separately introduced into a film forming section for forming a deposited film, and these are chemically reacted to form a material (hereinafter referred to as “FOCVD method”). Abbreviated)
And the like, and can be formed by various thin film deposition methods. 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 possible to easily introduce hydrogen atoms (H) together with aluminum atoms (Al) and silicon atoms (Si). Therefore, 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, in order to form a lower layer by a glow discharge method, aluminum atoms (Al) can be basically supplied.
Al supply gas, Si supply gas capable of supplying silicon atoms (Si), H supply gas capable of supplying hydrogen atoms (H), and at least one of alkali metals, alkaline earth metals, and transition metals GS that can supply gas containing atoms and, if necessary, germanium atoms (Ge) and tin atoms (Sn)
c A supply gas, an X supply gas capable of supplying a halogen atom (X) as required, an oxygen, nitrogen, carbon supply gas as required, and an atom (M
c) A supply gas is introduced at a desired gas pressure state into a deposition chamber in which the inside can be reduced in pressure to generate a glow discharge in the deposition chamber, and a glow discharge is generated on the surface of a predetermined support previously set at a predetermined position. Then, a layer made of AlSiH or the like may be formed.

When formed by the sputtering method, for example, Ar, H
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 e or a mixed gas based on these gases. And an H supply gas capable of supplying hydrogen atoms (H), a gas containing at least one atom among alkali metals, alkaline earth metals and transition metals, and optionally germanium atoms (Ge) and tin Atom (Sn)
GSc supply gas that can be supplied, X supply material gas that can supply halogen atoms (X) as needed, and CNOc supply gas that can supply durability-adjusting atoms (CNOc) as needed And a gas for supplying atoms that can supply atoms for adjusting the image quality (Mc) if necessary, is introduced into a deposition chamber for sputtering, and if necessary, a gas for supplying Al that can supply aluminum atoms (Al). Gas and / or silicon atom (S
This is achieved by introducing a Si supply gas capable of supplying i) into a deposition chamber for sputtering, and forming a plasma atmosphere of a desired gas.

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

In the present invention, when the lower layer is formed, aluminum atoms (Al), silicon atoms (Si), hydrogen atoms (H), alkali metals, alkaline earth metals,
Transition metal, germanium atom (Ge) and tin atom (Sn) and halogen atom (X) optionally contained
And atoms for adjusting durability (CNOc) and atoms for adjusting image quality (Mc) (hereinafter collectively referred to as “atoms (AS
H)) to form a layer having a desired distribution in the thickness direction by changing the distribution concentration C in the thickness direction (glow discharge method, HRCVD method, FOCVD method).
In the case of the method, the atoms whose distribution concentration should be changed (Al, Si,
(H, X) The supply gas is formed by appropriately changing the gas flow rate according to a desired rate-of-change curve and introducing the gas into the deposition chamber.

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

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.

When formed by the sputtering method, atoms (Al, S
To change the distribution concentration C of (i, H, X) in the layer thickness direction to form a layer having a desired distribution state (depth profile) in the layer thickness direction, first, the case of the glow discharge method In the same manner as described above, the raw material for supplying atoms (Al, Si, H, X) is used in a gas state, and the gas flow rate is appropriately changed according to a desired change rate curve, and is introduced into the deposition chamber. .

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

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.

An atom having characteristics capable of achieving the object of the present invention (AlSi
In order to form the lower layer composed of H), it is necessary to appropriately set the gas pressure in the deposition chamber and the temperature of the support as desired.

Gas pressure in the deposition chamber, if be appropriately selected within an optimum range in accordance with the layer design usually 1 × 10 ^-5 to 10 Torr, preferably 1 × 10 ^-4 ~3Torr, optimally and 1 × 10 ^-4 ~1Torr Is preferred.

The support temperature (Ts) is appropriately selected in an optimum range according to the layer design, but is usually 50 to 600 ° C., preferably 100 to 40 ° C.
Desirably, it is 0 ° C.

In the present invention, when creating a lower layer composed of atoms (AlSiH) by the glow discharge method, discharge power supplied to the deposition chamber, if be appropriately selected within an optimum range in accordance with the layer design usually 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 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.

In the layer region of the upper layer in contact with at least the lower layer in the present invention, atoms for controlling conductivity (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), and germanium atoms (Ge) , Tin atoms (Sn) are not substantially contained. However, in the other layer regions of the upper layer, atoms controlling conductivity (M), carbon atoms (C),
At least one of a nitrogen atom (N), an oxygen atom (O), a germanium atom (Ge), and a tin atom (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).

In the layer region of the upper layer, at least one of atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), germanium atoms (Ge), and tin atoms (Sn) for controlling conductivity are provided. When contained, the atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), germanium atoms (Ge), and tin atoms (Sn) that control the conductivity are contained in the layer region. It may be uniformly distributed throughout, or may be contained evenly in the layer region, but may be contained in a state of being distributed unevenly in the layer thickness direction. Is also good.

However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary that the metal be contained in a uniform distribution without unevenness from the viewpoint of making the characteristics in the in-plane direction uniform.

In the upper layer according to the present invention, at least one atom of an alkali metal, an alkaline earth metal, and a transition metal may be uniformly distributed throughout the layer region, or may be distributed in the layer region. Although it is contained evenly, there may be a portion 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 that the metal be contained in a uniform distribution without unevenness from the viewpoint of making the characteristics in the in-plane direction uniform.

Further, a layer region (hereinafter abbreviated as “layer region (M)”) containing atoms (M) for controlling conductivity (hereinafter abbreviated as “atom (M)”), carbon atoms (C) and A layer region containing a nitrogen atom (N) and / or an oxygen atom (O) (hereinafter abbreviated as “atom (CNO)”) (hereinafter abbreviated as “layer region (CNO)”) and a germanium atom ( Ge) and / or tin atom (Sn) (hereinafter “atom (G
C) ”) (hereinafter referred to as“ layer region (G
S) ") and the layer region containing at least one atom among alkali metals, alkaline earth metals and transition metals may be substantially the same layer region, or at least each layer region. May be shared, or each layer region may not be substantially shared.

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) and the like, and B, Al, and Ga are particularly preferable. Specific examples of Group V atoms include P (phosphorus), As (arsenic), Sb (antimony), and Bi (bismuth), with P and As being particularly preferred. Specific examples of Group VI atoms include S (sulfur), Se (selenium), Te (tellurium), and Po (polonium), with S and Se being particularly preferred. In the present invention, the layer region (M) has atoms (M) for controlling conductivity.
By mainly containing a group III atom, a group V atom or a group VI atom as an effect of controlling the conductivity type and / or conductivity and / or the layer region (M)
The effect of improving the charge injecting property between the layer region other than the layer region (M) of the upper layer can be obtained. Layer area (M)
The content of the atom (M) for controlling the conductivity contained in the metal is preferably 1 × 10 ^{−3 to} 5 × 10 ⁴ atomic ppm, more preferably 1 × 10 ⁻² to 1 × 10 ⁴ atomic ppm, and is most suitable. 1 × 10 ^{-1 to} 5
It is desirably set to × 10 ³ atomic ppm. Especially layer area (M)
Has a carbon atom (C) and / or nitrogen atom (N) and / or oxygen atom (O) content of 1 ×
When the concentration is 10 ³ atomic ppm or less, the content of the atom (M) for controlling the conductivity contained in the layer region (M) is preferably set to 1 × 10 ⁻³ to 1 × 10 ³ atomic ppm. When the content of carbon atoms (C) and / or nitrogen atoms (N) and / or oxygen atoms (O) exceeds 1 × 10 ³ atomic ppm, the content of atoms (M) for controlling conductivity is contained. Preferably, the amount is 1 × 10 ^{-1 to} 5 × 10 ⁴ atomic ppm.

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

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

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

In the present invention, the content of at least one atom in the alkali metal, alkaline earth metal, and transition metal contained in the upper layer is preferably 1 × 10 ⁻³ to 1 × 10 ₄ atoms p
pm, more preferably 1 × 10 ^-2 to 1 × 10 ³ atomic ppm, and most preferably 5 × 10 ^{-2 to} 5 × 10 ² atomic ppm.

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

For example, in order to form an upper layer made of Non-Si (H, X) by a glow discharge method, basically, a gas for supplying Si capable of supplying silicon atoms (Si) and a gas for supplying hydrogen atoms (H ) And / or an X supply gas that can supply halogen atoms (X) and, if necessary, an M supply gas and / or M that can supply atoms (M) that control conductivity. Or a C supply gas capable of supplying carbon atoms (C) and / or an N supply gas capable of supplying nitrogen atoms (N) and / or an O supply gas and / or germanium capable of supplying oxygen atoms (O) A Ge supply gas capable of supplying atoms (Ge) and / or a Sn supply gas capable of supplying tin atoms (Sn) and / or an alkali metal,
A supply gas capable of supplying at least one atom of an alkaline earth metal or a transition metal is introduced under a desired gas pressure into a deposition chamber in which the inside can be reduced in pressure, and a glow discharge is generated in the deposition chamber, and a predetermined Non-Si on the surface of the predetermined lower layer
What is necessary is just to form the layer which consists of (H, X).

In the present invention, the thickness of the upper layer is from 1 to 130 from the viewpoint of obtaining desired electrophotographic properties and economical effects.
μm, preferably 3 to 100 μm, and most preferably 5 to 60 μm.

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

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

When the upper layer is formed by selecting a-Si (H, X) as Non-Si (H, X), the support temperature (Ts) is appropriately selected in an optimal range according to the layer design. Usually 50 ~
It is desirable that the temperature be 400 ° C, preferably 100 to 300 ° C. When poly-Si (H, X) is selected as the upper layer and non-Si (H, X) is selected, 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 support surface, that is, to form a film on the support by plasma CVD at a support temperature of, for example, about 250 ° C., and then subject the amorphous film to an annealing treatment. This is a method of making poly. The annealing treatment is performed by heating the support to 400 to 600 ° C.
For about 5 to 30 minutes, or by irradiating with a laser beam 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.

Examples of substances that can serve as the Al supply gas used in the present invention include AlCl ₃ , AlBr ₃ , AlI ₃ , Al (CH ₃ ) ₂ Cl, Al (C
_{H 3) 3, Al (OCH} 3) 3, Al (C 2 H 5) 3, Al (OC 2 H 5) 3, Al (i
−C ₄ H ₉ ) ₃ , Al (i−C ₃ H ₇ ) ₃ , Al (C ₃ H ₇ ) ₃ , Al (OC ₄ H ₉ )
_{No. 3} is effectively used. Further, these Al supply gases may be replaced with H ₂ , He, Ar, Ne as necessary.
May be used after being diluted with such a gas.

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

Many halogen compounds are effective as the halogen supply gas used in the present invention. For example, 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, BrF, ClF, ClF 3,} BrF 5, BrF 3, IF 3, IF 7, ICl, Interhalogen compounds such as IBr can be mentioned.

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

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, A desired amount of a hydrogen compound or a silicon compound gas containing a hydrogen atom (H) may be mixed with these gases to form a layer.

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

In the present invention, the 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, discharge is caused by coexisting H ₂ , or silicon hydride such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ and the above-mentioned Si supply gas in the deposition chamber. But you can do it.

A hydrogen atom (H) that can be contained in the present invention and / or
Alternatively, in order to control the amount of the halogen atom (X), for example, the temperature of the support and / or the introduction of the raw material used to contain the hydrogen atom (H) or the halogen atom (X) into the deposition apparatus system The amount to be discharged, the temperature of the discharge power support, and the like may be controlled.

In the present invention, in order to structurally introduce an atom (M) for controlling conductivity and an atom (Mc) for adjusting image quality, for example, a Group III atom, a Group V atom or a Group VI atom, it is necessary to form a layer. At this time, a raw material for supplying a Group III atom, a raw material for introducing a Group V atom or a raw material for supplying a Group VI atom in a gas state in the deposition chamber is used for forming an upper layer. Should be supplied together with the raw material. No.
The source material for supplying group III atoms, the source material for supplying group V atoms, or the source material for supplying group VI atoms may be gaseous at normal temperature and normal pressure or at least under conditions of layer formation. It is desirable to employ one that 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 H 12, B 6 H 14 borohydride such as, B
Examples include boron halides such as F ₃ , BCl ₃ , and BBr ₃ . Other examples include AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , and TlCl ₃ .

As the raw material for supplying group V atoms, the present invention effectively uses PH ₃ , P ₂
H _4, etc. of hydrogen phosphorus _{halides, PH 4 I, PF 3,} PF 5, PCl 3, PCl 5, PBr 3, PBr 5, P
Halogenated phosphorus such as I ₃ and the like. In addition, AsH ₃ , AsF ₃ ,
AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , B
iCl ₃ , BiBr _{3 and the} like can also be mentioned as effective 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 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,
Substances in a gaseous state or capable of being gasified, such as (C ₂ H ₅ ) ₂ Se, TeH ₂ , TeF ₆ , (CH ₃ ) ₂ Te, and (C ₂ H ₅ ) ₂ Te.

In addition, the atoms (Mc,
M) The raw material for supply may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

In the present invention, in order to structurally introduce a carbon atom (C), a nitrogen atom (N), or an oxygen atom (O), a raw material for supplying a carbon atom (C) or a nitrogen atom ( N) The source material for supply or the source material for oxygen atoms (O) may be supplied in a gaseous state into the deposition chamber together with other source materials for forming the upper layer. The raw material for supplying 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₎ , Methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ) and the like.

In addition, CF ₄ , CCl ₄ , CH ₃ CF can be supplied in addition to the supply of hydrocarbons (C) because halogen atoms (X) can be supplied.
_And halogenated carbon gas such as ₃ .

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 gasizable nitrogen, such as ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium (NH ₄ N ₃ ), nitrogen compounds and nitrogen compounds of azide Can be mentioned. In addition to this, in addition to the supply of nitrogen atoms (N), the supply of halogen atoms (X) can be performed, so that nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), etc. Nitrogen halide compounds can be mentioned.

Starting materials that are effectively used as possible source gases for supplying oxygen atoms (O) include, for example, oxygen (O ₂ ), ozone (O ₃ ), nitric oxide (NO), and nitrogen dioxide (NO ₂ ). ,
Nitrogen monoxide (N ₂ O), nitrogen trioxide (N ₂ O ₃ ), nitrogen tetraoxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂ O ₅ ), nitrogen trioxide (NO ₃ ), silicon atom ( For example, lower siloxanes such as disiloxane (H ₃ SiOSiH ₃ ) and trisiloxane (H ₃ SiOSiH ₂ OSiH ₃ ) having Si), an oxygen atom (O), and a hydrogen atom (H) as constituent atoms may be mentioned. it can.

In the present invention, in order to introduce germanium (Ge) or tin atom (Sn) structurally, a raw material for supplying germanium (Ge) or tin atom (S
n) 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. Source materials for supplying germanium (Ge) or tin atoms (Sn) can be:
It is desirable to employ a material which is gaseous at normal temperature and normal pressure or can be easily gasified at least under the conditions for forming the layer.

GeH ₄ , Ge ₂ H ₆ , G
e ₃ H ₈ , Ge ₄ H ₁₀ and other gaseous or gasifiable germanium hydrides can be used effectively.Especially, ease of handling during layer formation work, good Ge supply efficiency, etc. In this regard, GeH ₄ , Ge ₂ H ₆ , and Ge ₃ H ₈ are preferred.

In addition, GeHF ₃ , GeH ₂ F ₂ , GeH ₃ F, GeHCl ₃ , GeH ₂ Cl ₂ , GeH ₃ C
l, GeHBr ₃ , GeH ₂ Br ₂ , GeH ₃ Br, GeHI ₃ , GeH ₂ I ₂ , GeH ₃ I, etc., hydrogenated germanium halides, GeF ₄ , GeCl ₄ , GeBr ₄ , GeI ₄ , Ge
_{F 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 ₂ H ₆ , Sn ₃
Cited as H _8, Sn ₄ tin hydride which may or gasified gas conditions such as H ₁₀ is effectively used, in particular the layer created when working easy handling, in view of good such as the Sn supply efficiency , Sn
H ₄ , Sn ₂ H ₆ and Sn ₃ H ₈ are preferred.

In addition, SnHF ₃ , SnH ₂ F ₂ , SnH ₃ F, SnHCl ₃ , SnH ₂ Cl ₂ , SnH ₃ C
_{l, 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.

In the present invention, when containing at least one atom among alkali metals, alkaline earth metals, and transition metals, for example, in order to structurally introduce copper atoms (Cu), copper atoms (Cu The raw material for supply may be introduced in a gaseous 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 terms of easy handling at the time of forming a layer and high supply efficiency of Cu, etc., bisdimethylglyoximato copper (II) Cu (c ₄
H ₇ N ₂ O ₂ ) ₂ is mentioned as a preferable example.

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. For example, in order to structurally introduce a sodium atom (Na), a yttrium atom (Y), a manganese atom (Mn), or a zinc atom (Zn), a raw material for sodium atom (Na) introduction or A raw material for introducing yttrium atoms (Y), a raw material for introducing manganese atoms (Mn), or a raw material for introducing zinc atoms (Zn) in a gaseous state in the deposition chamber is used for forming another upper layer. What is necessary is just to introduce with a raw material. The raw material for introducing sodium atoms (Na), the raw material for introducing yttrium atoms (Y), the raw material for introducing manganese atoms (Mn), or the raw material for introducing zinc atoms (Zn) include: It is desirable to employ a material which is gaseous at normal temperature and normal pressure or can be easily gasified at least under the conditions for forming the layer.

As a substance which can be a gas for introducing Na, an organic metal containing sodium amine (NaNH ₂ ) or a sodium atom (Na) can be effectively used. Sodium amine (NaNH ₂ ) is mentioned as a preferable one in terms of good introduction efficiency and the like.

As a substance that can be a Y-introducing gas, an organic metal containing an yttrium atom (Y) can be effectively used, and in particular, it is easy to handle at the time of forming a layer and has a high Y-introducing efficiency. in, triisopropanolamine yttrium _{Y (Oi-C 3 H 7} ) 3 can be mentioned as preferred.

As a substance that can be a Mn introduction gas, an organic metal containing a manganese atom (Mn) can be effectively used. In particular, it is easy to handle at the time of forming a layer and has a high Mn introduction efficiency. With monomethylpentacarbonylmanganese Mn
(CH ₃ ) (CO) ₅ is preferred.

As a substance that can be a gas for introducing Zn, a zinc atom (Z
The organic metal containing n) is effectively used. Particularly, diethyl zinc Zn (C ₂ H ₅ ) ₂ is preferable from the viewpoints of easy handling at the time of forming a layer and good Zn introduction efficiency. Are listed.

Further, these Na-introduced gas, Y-introduced gas, Mn-introduced gas, or Zn-introduced gas may be replaced with H ₂ , He,
It may be diluted with a gas such as Ar or Ne before use.

In order to structurally introduce magnesium atoms (Mg), when forming a layer, a raw material for supplying magnesium atoms (Mg) is in a gas state in a deposition chamber, and another raw material for forming an upper layer is formed. It should be introduced together with. 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 conditions for forming a layer is desirable.

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 a bis (cyclopentadienyl) magnesium (II) complex salt (Mg (C ₅ H ₅ ) ₂ ) is preferred.

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.

〔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 The light receiving member for electrophotography of the present invention was formed by a high frequency (hereinafter abbreviated as “RF”) glow discharge decomposition method.

FIG. 3 shows an apparatus for manufacturing a light receiving member for electrophotography by a RF glow discharge decomposition method, comprising a source gas supply device 1020 and a deposition device 1000.

Source gas for forming each layer of the present invention is sealed in the closed container of the gas cylinder 1078 of 1071, 1072, 1073, 1074, 1075, 1076, 1077, 1079, and the closed container of 1080 in the figure. , 1071 is a cylinder of SiH ₄ gas (99.99% purity), 1072 is a cylinder of H ₂
Gas (purity 99.9999%) cylinder, 1073 is CH ₄ gas (purity 9
9.999%) cylinder, 1074 is GeH ₄ gas (purity 99.999%) cylinder, 1075 is B ₂ H ₆ gas (purity 99.999 purity) diluted with H ₂ gas
%, Hereinafter abbreviated as “B ₂ H ₆ / H ₂ ”), 1076 is a NO gas (purity 99.9%) cylinder, 1077,1079 is a He gas (purity 99.999)
%) Cylinder, 1078 is a sealed container filled with Al (CH ₃ ) ₃ (purity 99.99%), and 1080 is a sealed container filled with NaNH ₂ (purity 99.9%).

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 of gas cylinders 1071 to 1077 and 1079
~ 1058, the inflow valves 1031 ~ 1038, the leak valve 1015 of the deposition chamber 1001 is closed, and the outflow valves 1041 ~ 1048, the auxiliary valve 1018 are opened. The valve 1016 was opened, and the inside of the deposition chamber 1001 and the inside of 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
72 from the H ₂ gas, CH ₄ gas from the gas cylinder 1073, GeH ₄ gas from the gas cylinder _{1074, B 2 H 6 / H} 2 gas from the gas cylinder 1075, NO gas from the 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 contour rollers 1021 to 1028. At this time, the He gas from the gas cylinder 1077 passes through the sealed container 1078 filled with Al (CH ₃ ) ₃ to the mass flow controller 1027.
₃ ) _Three gases (hereinafter abbreviated as “Al (CH ₃ ) ₃ / He”) are introduced, and the mass flow controller 1028 has a gas cylinder 10
Since He gas from 79 to come through the closed container 1080 which full of NaNH ₂ NaNH ₂ diluted with He gas (hereinafter "NaNH ₂ / H
e ").

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

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

To form the lower layer, the outflow valves 1041, 1042, 1047, 1
048 and gradually open the SiH ₄ gas auxiliary valve 1018, H ₂
Gas, Al (CH ₃ ) ₃ / He gas, NaNH ₂ / He gas 1
008 was discharged into the deposition chamber 1001 through the gas discharge holes 1009. At this time, the flow rate of the SiH ₄ gas was 5 sccm, and the flow rate of the H ₂ gas was 10 sccm.
m, the mass flow controllers 1021, 1022, 1027, and 1028 were adjusted so that the flow rate of the Al (CH ₃ ) ₃ / He gas was 120 sccm and the flow rate of the NaNH ₂ / He gas was 10 sccm. The opening of the main valve 1016 was adjusted while watching the vacuum gauge 1017 so that the pressure in the deposition chamber 1001 became 0.4 Torr. Thereafter, the high-frequency matching box 1 sets the power of the RF power source (not shown) to 5 mW / cm ³
RF power was introduced into the deposition chamber 1001 through 012 to generate RF glow discharge, and the formation of the lower layer on the cylindrical aluminum-based support was started. During the formation of the lower layer, the SiH ₄ gas flow rate
From to increase at a constant rate to 50 sccm 5 sccm, as H ₂ gas flow rate increases at a constant rate 200sccm from _{10sccm, Al (CH 3) 3} / He gas flow rate at a constant rate 40sccm from 120sccm as reduced, NaNH ₂ / He gas flow rate 10sccm
Mass flow controller 102
Adjusting 1,1022,1027,1028 and stopping the RF glow discharge when the lower layer with the layer thickness of 0.05μm was formed.
1041, 1042, 1047, 1048 and auxiliary valve 1018 are closed,
The flow of gas into the deposition chamber 1001 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 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 SiH ₄ gas flow rate
300 sccm, H ₂ gas flow rate was adjusted with mass flow controllers 1021 and 1022 of each so that the 300 sccm. Deposition chamber 1001
The opening of the main valve 1016 was adjusted while watching the vacuum gauge 1017 so that the internal pressure became 0.5 Torr. Thereafter, not illustrated in the power of the RF power source was set to 15 mW / cm ³ was introduced RF power to the deposition chamber 1001 through the high-frequency matching I scan 1012, to rise to RF glow discharge, a first upper layer on the lower layer The formation of the layer region was started, the RF glow discharge was stopped when the first layer region of the upper layer having a layer thickness of 20 μm was formed, and the outflow valves 1041 and 1042 and the auxiliary valve 1018 were closed.
The flow of gas into 1 was stopped, and the formation of the first layer region of the upper layer was completed.

Next, to form the second layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened and the SiH
_Four gases and CH ₄ 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, the mass flow controllers 1021 and 1023 adjusted the flow rates of the SiH ₄ gas to 50 sccm and the flow rate of the CH ₄ gas to 500 sccm. Deposition chamber 100
The opening of the main valve 1016 was adjusted while watching the vacuum gauge 1017 so that the pressure in 1 became 0.4 Torr. After that, the power of the RF power supply (not shown) was set to 10 mW / cm ³ and RF power was introduced into the deposition chamber 1001 through the high-frequency matching box 1012, and RF power was supplied.
Generate a glow discharge, start forming a second layer region on the first layer region of the upper layer, stop the RF glow discharge when the second layer region of the upper layer having a thickness of 0.5 μm is formed, Also, close the outflow valves 1041 and 1043 and the auxiliary valve 1018,
The flow of gas into the deposition chamber 1001 was stopped, and the formation of the second 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.

In forming the Comparative Example 1 lower layer, other than not using H ₂ gas was prepared an electrophotographic light-receiving member by the same production conditions of Example 1.

The distribution of the content of atoms contained in the thickness direction in the vicinity of the lower layer of the electrophotographic light-receiving member of Example 1 and Comparative Example 1 was determined by SIMS (secondary ion mass spectrometer, IMS-manufactured by Kameka). 3F). The results are shown in FIGS. 4 (a) and 4 (b). In FIG. 4, the horizontal axis represents the measurement time and corresponds to the position in the layer thickness direction. The vertical axis represents the content of each atom as a relative value.

FIG. 4 (a) shows the distribution of the content of atoms contained in Example 1 in the layer thickness direction, where aluminum atoms are more distributed on the support side and silicon atoms and hydrogen atoms are distributed more on the upper layer side. Was.

FIG. 4 (b) shows the distribution of the content of atoms contained in Comparative Example 1 in the layer thickness direction, where aluminum atoms are more distributed on the support side, silicon atoms are more distributed on the upper layer side, and hydrogen is distributed. The atoms were uniformly distributed.

Next, the prepared electrophotographic light-receiving members of Example 1 and Comparative Example 1 were respectively set in an electrophotographic apparatus in which a Canon copier NP-7550 was modified for an experiment, under various conditions. Some electrophotographic properties were checked.

Using a magnet roller as a cleaning roller, coat the magnet roller with a positive toner,
The photoreceptor for electrophotography was rotated 1000 times while all the chargers were not operated. Next, by using a normal electrophotographic process, an image was formed using a black original and the number of spots was measured. As a result, the light receiving member for electrophotography of Example 1 was better than the light receiving member for electrophotography of Comparative Example 1. It turned out that the number of spots was less than 1/3.

In addition, the light receiving member for electrophotography is placed in a state in which an abnormal discharge occurs due to a lump of paper powder placed on the grit of the separation charger.
Rotated. Next, the paper dust was removed, an image was formed using a black document, and the number of spots was measured. As a result, the light receiving member for electrophotography of Example 1 was 2 times smaller than the light receiving member for electrophotography of Comparative Example 1. It turned out that the number of spots was less than / 3.

In addition, high-density polyethylene made diameter about 32mmφ, thickness 5m
An m roller was pressed against the electrophotographic light receiving member at a pressure of about 2 kg, and the electrophotographic light receiving member was rotated 500,000 times. Next, as a result of comparing the number of occurrences of peeling of the light receiving layer by visual observation, the number of occurrences of peeling of the electrophotographic light receiving member of Example 1 which is less than 1/2 of that of the electrophotographic light receiving member of Comparative Example 1 was smaller. It turned out that it became.

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 1.

[Example 2] An electrophotographic light-receiving member as in Example 1 under the conditions shown in Table 1 except that the gas flow rate of Al (CH ₃ ) ₃ / He was changed to the value shown in Table 2. It was created.

[Comparative Example 2] A light receiving member for electrophotography in the same manner as in Example 1, except that the gas flow rate of Al (CH ₃ ) ₃ / He was changed to the value shown in Table 2. It was created.

In the same manner as in Example 1, the produced electrophotographic light-receiving members of Example 2 and Comparative Example 2 were pressed against a high-density polyethylene roller to compare the number of peeled layers. The results are shown in Table 2 assuming that the number of occurrences of layer peeling of the electrophotographic light-receiving member of Example 1 is 1. Furthermore, the content of aluminum atoms near the upper part of the lower layer was analyzed by SIMS. Table 2 shows the results.

As shown in Table 2, in the region where the content of aluminum atoms in the vicinity of the upper portion of the lower layer was 20 atomic% or more, a favorable effect of reducing the number of occurrences of layer peeling was obtained.

Example 3 During the formation of the lower layer, the temperature of the support was changed at a constant rate from 350 ° C. to 250 ° C., and Y (Oi—C ₃ H ₇ ) ₃ was changed to NaNH _2.
A photoreceptor for electrophotography was prepared in the same manner as in Example 1 under the conditions shown in Table 1 except that was used, and the same evaluation was carried out. A good effect was obtained which was improved with respect to.

During the formation of the Example 4 the lower layer, 5 mW / cm ³ RF power from 50 mW / cm ³
It is changed at a predetermined rate to, Mn (CH ₃₎ instead of NaNH ₂ (C
O) An electrophotographic light-receiving member was prepared in the same manner as in Example 1 except that the preparation conditions shown in Table 1 were used except for using ₅ .
As a result of performing the same evaluation, a favorable effect of improving spotting and layer peeling was obtained as in Example 1.

Example 5 Example ₁ was repeated under the same conditions as in Example 1 except that Zn (C ₂ H ₅ ) ₂ was used instead of NaNH ₂ , and the raw material gases shown in Table 3 were further added. Similarly, an electrophotographic light-receiving member was prepared and subjected to the same evaluation. As in Example 1, a favorable effect of improving spotting and layer peeling was obtained.

Example 6 Except that the outer diameter of the cylindrical aluminum-based support was 30 mm and the gas flow rate and RF power shown in Table 1 were each reduced to 1/3, the procedure was carried out under the preparation conditions shown in Table 1. A light-receiving member for electrophotography was prepared in the same manner as in Example 1, and the same evaluation was carried out. As a result, similar effects to those in Example 1 were obtained.

Example 7 Under the conditions shown in Table 4, an electrophotographic light-receiving member was prepared in the same manner as in Example 1, and the same evaluation was performed. A good effect was obtained which was improved.

Example 8 The light receiving member for electrophotography of the present invention was formed by a microwave (hereinafter abbreviated as “μW”) glow discharge decomposition method.

The deposition apparatus 1000 of the RF glow discharge decomposition method manufacturing apparatus shown in FIG. 3 was converted to the μW glow discharge decomposition method deposition apparatus 1100 shown in FIG. 6 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 so-called surface on which the mirror-finished cylindrical aluminum-based support is continuously exposed to a large number of bearing spheres falling to form countless dents on the surface of the cylindrical aluminum-based support. After dimple processing, c = 50 μm and d = 1 μm in the cross-sectional shape as shown in FIG.
Cylindrical aluminum-based support with an outer diameter of 10
8 mm.

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
1,1042,1044,1047,1048 and auxiliary valve 1018 are gradually opened to introduce SiH ₄ gas, H ₂ gas, SiF ₄ gas, Al (CH ₃ ) ₃ / He gas, NaNH ₂ / He gas into gas introduction pipe 1110 (Not shown) into the plasma generation region 1109. At this time, the SiH ₄ gas flow rate was 15 sccm, the H ₂ gas flow rate was 20 sccm, and the SiF ₄ gas flow rate was 20 sccm.
Gas flow rate is 10 sccm, Al (CH ₃ ) ₃ / He gas flow rate is 400 sccm,
The mass flow controllers 1021, 1022, 1024, 1027, and 1028 adjusted the NaNH ₂ / He gas flow rate to 20 sccm. The opening of the main valve (not shown) was adjusted while watching the vacuum gauge (not shown) so that the pressure in the deposition chamber 1101 became 0.6 mTorr. Thereafter, the power of a μW power supply (not shown) was set to 0.5 W / cm ³ , and μW power was introduced into the plasma generation region 1109 through the waveguide 1103 and the dielectric window 1102 to generate a μW glow discharge, and the cylindrical aluminum The formation of the lower layer on the system support 1107 was started. During the formation of the lower layer, the SiH ₄ gas flow rate was 15
As increases from sccm to 150sccm at a constant rate, as H ₂ gas flow rate increases at a constant rate 300sccm from 20sccm, as SiF ₄ gas flow rate increases at a constant rate 20sccm from 10 sccm, Al (CH ₃ ) ₃ / He gas flow rate from 400sccm
So as to decrease at a constant rate to 50sccm, NaNH ₂ / He gas flow rate by adjusting the mass flow controller 1021,1022,1024,1027,1028 to be constant flow rate of 20 sccm, a layer thickness 0.07μ
When the lower layer of m is formed, the μW glow discharge is stopped,
Further, the outflow valves 1041, 1042, 1044, 1047, 1048 and the auxiliary valve 1018 were closed to stop the flow of gas into the plasma generation region 1109, 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 and the auxiliary valve 1018 are gradually opened, and SiH ₄ gas, H ₂ gas, and SiF ₄ gas are supplied to the gas introduction pipe 1110. The gas was introduced into the plasma generation space 1109 through a gas discharge hole (not shown). At this time, the mass flow controllers 1021, 1022, 1024 adjusted the flow rates of the SiH ₄ gas to 700 sccm, the flow rate of the H ₂ gas to 500 sccm, and the flow rate of the SiF ₄ gas to 30 sccm. The pressure in the deposition chamber 1101 was adjusted to be 0.5 mTorr.
Thereafter, the power of a μW power supply (not shown) was set to 0.5 W / cm ³ , and a μW glow discharge was generated in the plasma generation chamber 1109 in the same manner as in the lower layer, and the first layer region of the upper layer was formed on the lower layer. Was formed, and a first layer region of an upper layer having a layer thickness of 20 μm was formed.

Next, to form the second layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened and the SiH
_Four gases and CH ₄ gas were introduced into the plasma generation space 1109 through gas discharge holes (not shown) of the gas introduction pipe 1110. At this time, the mass flow controllers 1021 and 1023 adjusted the flow rates of the SiH ₄ gas to 150 sccm and the flow rate of the CH ₄ gas to 500 sccm. The pressure in the deposition chamber 1101 was 0.3 mTorr. Then, 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 first layer region of the upper layer. A two layer region was formed.

Table 5 shows the conditions for forming the light receiving member for electrophotography 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.

FIG. 4 (c) shows the result of SIMS analysis of the distribution of the atoms contained in the vicinity of the lower layer in the layer thickness direction in the same manner as in Example 1.

As in Example 1, it was found that hydrogen atoms of silicon atoms of aluminum atoms were distributed.

Example 9 The lower layer of the electrophotographic light-receiving member of the present invention was formed by RF sputtering, and the upper layer was formed by PF glow discharge decomposition.

FIG. 8 shows an apparatus for producing a light receiving member for electrophotography by a PF sputtering method, comprising a source gas supply device 1500 and a deposition device 1501.

In the figure, 1045 is Si, Al, which is a raw material for forming the lower layer.
The target is made of Mn, and the mixing ratio in the thickness direction is changed so that each atom has a desired distribution state.

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

In the figure, reference numeral 1402 denotes a cylindrical aluminum-based support having an outer diameter of 108 mm and a mirror-finished surface.

First, as in Example 1, the inside of the deposition chamber 1401 and the gas pipe were evacuated until the pressure in the deposition chamber 1401 became 1 × 10 ⁻⁶ Torr.

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

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

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

To form the lower layer, SiH ₄ gas by opening gradually the outflow valves 1420,1421,1422 and auxiliary valve 1432, H ₂ gas,
Ar gas was caused to flow into the deposition chamber 1401. At this time, the flow rate of the SiH ₄ gas was 10 sccm, the flow rate of the H ₂ gas was 5 sccm, and the flow rate of the Ar gas was 200 sccm.
cm each mass flow controller 1412,1
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 start formation of a lower layer on the cylindrical aluminum-based support. During the formation of the lower layer, the SiH ₄ gas flow rate is 10 sc
to increase at a constant rate from cm to 50 sccm, as H ₂ gas flow rate increases at a constant rate 100sccm from 5 sccm,
Ar gas flow rate was adjusted to a constant flow rate of 200 sccm mass flow controllers 1412, 1413, 1414, layer thickness 0.05μ
When the lower layer of m was formed, the RF glow discharge was stopped, the outflow valves 1420, 1421, 1423 and the auxiliary valve 1432 were closed, the flow of gas into the deposition chamber 1401 was stopped, and the formation of the lower layer was completed. .

Table 6 shows the conditions for forming the light receiving member for electrophotography described above.

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, in order to form the upper layer, a light receiving member for electrophotography was prepared in the same manner as in Example 1 by using the apparatus shown in FIG. 3 under the preparation conditions shown in Table 1, and the same evaluation was performed. As a result, as in Example 1, a favorable effect of improving spotting and layer peeling was obtained.

FIG. 4D shows the result of analyzing the distribution of the content of atoms contained in the vicinity of the lower layer in the thickness direction in the same manner as in Example 1 by SIMS.

As in Example 1, it was found that aluminum atoms, silicon atoms, and hydrogen atoms were distributed.

[Summary of the effects of the invention] The electrophotographic light-receiving member of the present invention has a specific layer structure as described above, thereby solving all the problems in the conventional electrophotographic light-receiving member composed 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, an alkali metal,
As a remarkable feature by containing at least one atom of an alkaline earth metal or a transition metal, a hydrogen atom and a halogen atom contained in the lower layer can be more dispersed, and an aggregate of the hydrogen atom and / or the halogen atom can be used. In addition, it is possible to prevent the peeling of the film that occurs during long use.

Furthermore, since the charge (photocarrier) injection and adhesion between the aluminum-based support and the upper layer and the charge (photocarrier) travelability in the lower layer are significantly improved, image characteristics and It is characterized by a remarkable improvement in durability, resulting in improved production stability and quality stability.

[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. , Third
The figure is an example of an apparatus for forming a light receiving layer of an electrophotographic light receiving member of the present invention, and is a schematic explanatory view of a manufacturing apparatus by a glow discharge method using RF, and FIG. 4 is an example of the present invention. SI
FIG. 9 is an explanatory diagram of the analysis results of MS. FIG. 5 is an enlarged view of a cross section of the aluminum-based support when the surface of the aluminum-based support for forming the electrophotographic light-receiving member of the present invention is subjected to so-called dimple processing, and FIG. FIG. 7 is a schematic explanatory view of a deposition apparatus when a microwave glow discharge method is used to form a light receiving layer of the light receiving member. FIG. 7 shows a light receiving layer of the light receiving member for electrophotography according to the present invention. FIG. 8 is a schematic explanatory view of a manufacturing apparatus by a glow discharge method using a microwave as an example of an apparatus for forming a light receiving layer of an electrophotographic light receiving member of the present invention. FIG. 3 is a schematic explanatory view of a manufacturing apparatus by an RF sputtering method. 1, 100 ... the light receiving member for electrophotography of the present invention, 101 ... aluminum-based support, 102 ... light receiving layer,
103: lower layer, 104: upper layer, 105: free surface. 2. Referring to FIG. 2, reference numeral 200 denotes a conventional light receiving member for electrophotography, 201 denotes an aluminum-based support, 202 denotes a photosensitive layer made of A-Si, and 203 denotes a free surface. Referring to FIG. 3, 1000: deposition apparatus by RF glow discharge decomposition method, 1001: deposition chamber, 1005: cylindrical aluminum-based support, 1008: gas introduction pipe, 1009: gas discharge hole,
1012 …… High frequency matching box, 1014 …… Heating heater, 1015 …… Leak valve, 1016 …… Main valve,
1017 Vacuum gauge, 1018 Auxiliary valve, 1020 Source gas supply device, 1021-1027 Mass flow controller, 1031-1037 Gas inflow valve, 1041-1047 Gas outflow valve, 1051-1057 ... Valve for raw gas cylinder, 1061-1067 ... Pressure regulator, 1071-1077 ... Gas cylinder for raw material, 1078 ... A sealed container for raw material. 6 and 7, reference numeral 1100 denotes a deposition apparatus by a microwave glow discharge method; 1101 a deposition chamber; 1102 a dielectric window; 1103 a waveguide; , 1109: Plasma generation area, 1010: Gas introduction pipe. In FIG. 8, 1401: deposition chamber, 1402: cylindrical aluminum-based support, 1405: target, 1407: main valve, 1408 to 1410: raw material gas cylinder, 1412 to 1414
…… Mass flow controller, 1416-1418 …… Gas inflow valve, 1420-1422 …… Gas outflow valve, 1432 …… Auxiliary valve, 1433 …… High frequency matching box, 1435…
... Vacuum gauge, 1500 ... Source gas supply device, 1501 ... Deposition device by RF sputtering method.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroaki Shinno 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Masafumi Sano 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (56) References JP-A-62-192751 (JP, A) JP-A-1-3668 (JP, A) JP-A-61-112155 (JP, A) JP-A-62-1554 (JP, A) A) JP-A-59-212845 (JP, A) JP-A-58-111046 (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. Atoms, a silicon atom, a hydrogen atom and / or a halogen atom, and is composed of an inorganic material containing at least one of an alkali metal atom, an alkaline earth metal atom, and a transition metal atom. The silicon atoms and hydrogen atoms and / or halogen atoms both increase from the aluminum support toward the top, and the content of the aluminum atoms is 20 atomic% near the top. The lower layer described above and a silicon atom as a parent and at least one of a hydrogen atom and a halogen atom Light-receiving member, characterized in that towards an upper layer composed of non-single-crystal material containing.