JPS63274965A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To improve the resolution, durability, and productivity of the title member by forming the photoreceptive layer consisting of a lower layer of the inorg. member contg. specified atoms in specified distribution and an upper layer of the non-single crystal material contg. specified atoms and contg. a specified atom at the contact region with the lower layer on an Al supporting body. CONSTITUTION:The photoreceptive layer 102 consisting of the lower layer 103 of the inorg. material contg. the Al atom, H atom, and Si atom unevenly distributed in the thickness direction and contg. CNOc atom for regulating durability and the upper layer 104 of the non-crystal material with an Si atom as the matrix contg. at least one between an H atom and a halogen atom, and contg. at least one among a C atom, an N atom, and an O atom at the contact region with the layer 103 is formed on the Al supporting body 101, and hence the resolution, durability, and productivity are enhanced. In addition, the adhesion between the layers 103 and 104 is increased by the H atom, N atom, and O atom, the picture image defect is controlled, and the durability is further improved.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to electromagnetic waves such as light (here, light in a broad sense, meaning ultraviolet rays, visible light, infrared rays, X-rays, γ-rays, etc.). The present invention relates to a photoreceptor member that is sensitive to light.

[Prior art]

In the field of image formation, photoconductive materials constituting the photoreceptive layer of photoreceptive members are highly sensitive, have a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], and have a high sensitivity to the spectral characteristics of the electromagnetic waves to be irradiated. It has suitable absorption spectrum characteristics, fast photoresponsiveness, and desired dark resistance value.
Characteristics such as being non-polluting to the human body during use are required. Particularly in the case of an electrophotographic light receiving member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-pollution during use is an important point.

Based on this point, amorphous silicon (hereinafter referred to as A-8i) is a photoconductive material that has recently attracted attention.
Application as a light-receiving member for electrophotography is described in Japanese Patent No. 855718 and the like.

FIG. 2 is a sectional view schematically showing the layer structure of a conventional electrophotographic light-receiving member, in which 201 is an aluminum support and 2'02 is a photosensitive layer made of A-3i. Such electrophotographic light-receiving members are generally produced by heating an aluminum support 201 to 50°C to 350°C, and forming a film on the support by vapor deposition, thermal CVD, plasma CVD, sputtering, or the like. A photosensitive layer 202 made of A-8i is created.

However, in this electrophotographic moonlight receiving member, since the thermal expansion coefficients of aluminum and A-8i are different by one order of magnitude, cracks and peeling may occur in the A-Si photosensitive layer 202 during cooling after film formation, which is a problem. It becomes. In order to solve these problems, JP-A-59-28162 proposes an electrophotographic photoreceptor consisting of an aluminum support, an intermediate layer containing at least aluminum, and an A-8i photoreceptor. The aluminum-based support and A-3i are separated by an intermediate layer containing at least aluminum.
It relieves the stress caused by the difference in thermal expansion coefficients of the A-3i Nausea and reduces cracking and peeling of the A-3i Nausea.

[Problem that the invention seeks to solve]

However, electrophotographic light-receiving members having a light-receiving layer made of conventional A-8t have electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and use environment characteristics. Individual improvements have been made in terms of stability, stability over time, and durability.
The reality is that there is room for further improvement in terms of improving overall characteristics.

For example, in recent years, improvements have been made to optical exposure devices, developing devices, transfer devices, etc. in electrophotographic devices to improve the image characteristics of electrophotographic devices, and as a result, the image characteristics of light-receiving members for electrophotography have also improved more than ever before. is now in demand.

In particular, as a result of improved image resolution, there is a reduction in non-uniformity in fine areas of image density, commonly known as "roughness", and a reduction in image defects in the form of black or white spots, commonly known as "pots". In particular, there has been a need to reduce "pots" of minute size, which were not considered a problem in the past.

Furthermore, when the electrophotographic light receiving member comes into contact with foreign matter that has entered the electrophotographic device, or when the electrophotographic light receiving member comes into contact with the electrophotographic device itself or maintenance tools during maintenance of the electrophotographic device, There have been problems such as the durability of the electrophotographic light-receiving member being impaired due to the occurrence of image defects and peeling of the A-8t film due to the impact mechanical pressure applied for a relatively short period of time.

Furthermore, due to the stress generated due to the difference in thermal expansion coefficient between the aluminum support and the A-8t film, cracks and peeling occur in the A-8i film, resulting in a reduction in productivity and yield.

Therefore, while efforts are being made to improve the properties of the A-3i material itself, when designing an electrophotographic light receiving member, it is important to consider It is necessary to make improvements from this perspective.

[Means and effects for solving the problems] The electrophotographic light-receiving member of the present invention comprises an aluminum-based support and an electron-based photoreceptor layer having a multilayer structure having at least photoconductivity on the support. In the photographic light-receiving member, the light-receiving layer contains at least aluminum atoms (A1), silicon atoms (Si), hydrogen atoms (H), and durability adjusting atoms (CNOC') as constituent elements from the support side. The aluminum atom (A1) and the silicon atom (S
i) and hydrogen atoms (H) in a non-uniform distribution in the layer thickness direction;
) as the base, hydrogen atom ()I) and halogen atom (
(H, X) (hereinafter abbreviated as "rNon-8t (H, and an upper layer containing at least one of nitrogen atoms (N) and oxygen atoms (0).

The electrophotographic light-receiving member of the present invention designed to have the above-described layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical properties, optical properties, and photoconductive properties. , durability, image characteristics, and use environment characteristics.

In particular, in the lower layer, aluminum atoms, silicon atoms, and especially hydrogen atoms are contained in a non-uniform distribution state in the layer thickness direction, and durability-adjusting atoms (CNOc) are contained in the aluminum-based support. The ability to inject charge (photocarriers) between the aluminum support and the upper layer is improved, and the structural continuity of the constituent elements between the aluminum support and the upper layer is also improved, so roughness and spots are eliminated. It is possible to stably and repeatedly obtain high-quality images with improved image characteristics, clear halftones, and high resolution.

Furthermore, as a distinctive feature of the durability-adjusting atom content,
The resistance to relatively short-term impact mechanical pressure applied to electrophotographic light-receiving members has been significantly improved, and image defects and peeling of the Non-3i (H,X) film can be prevented. The durability is further improved, and the stress generated due to the difference in thermal expansion coefficient between the aluminum support and the Non-5i (■,
It is possible to prevent the occurrence of cracks and peeling in the H,

Furthermore, in the present invention, the quality of the upper layer is improved by containing at least one atom among carbon atoms, nitrogen atoms, and oxygen atoms in the layer region in contact with the lower layer, thereby improving the durability against high voltage. Improved sex,
Since the adhesion between the upper layer and the lower layer is further improved, peeling of the Non-8i (H,X) film, which causes image defects, is prevented and durability is improved.

In addition, although it is mentioned in the above-mentioned Japanese Patent Application Laid-Open No. 59-28162 that aluminum atoms and silicon atoms are contained unevenly in the layer thickness direction, and that hydrogen atoms are also contained, There is no mention of how it is written, and it is clearly distinguished from the present invention.

[Detailed description of the invention]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic light-receiving member of the present invention will be described in detail below with reference to the drawings.

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

The electrophotographic light-receiving member 100 shown in FIG. The lower layer 103 has a portion containing non-uniform distribution in the direction;
an upper layer 104 composed of Si (H, The photoreceptive layer 102 has a layer structure consisting of: Top layer 104 has a free surface 105.

Aluminum support 101 used in the present invention
An aluminum alloy is used as the material. There are no particular limitations on the alloy components including the substrate aluminum in the aluminum alloy of the present invention, and the types, compositions, etc. of the components can be arbitrarily selected. Therefore, the aluminum alloy of the present invention has Japanese Industrial Standards (J
Pure aluminum, Al-Cu, which is standardized or registered as wrought material, casting, die casting, etc. in IS), AA standards, BS standards, DIN standards, international alloy registration, etc.
system, Al-Mn system, Al-3i system, Al-Mg system, Al
- Alloys with compositions such as Mg-3i series, Al-Zn-Mg series, etc., Al-Cu-Mg series (duralumin, super duralumin, etc.), Al-Cu-5i series (Lautal etc.), Al-
Contains Cu-Ni-Mg type (Y alloy, RR gold alloy), aluminum powder sintered body (SAP), etc.

Incidentally, although the specific composition of the aluminum alloy of the present invention is illustrated below, this is only an example of the present invention, and the present invention is not limited to the following example.

Examples of pure aluminum include JISIloo,
Si and Fe 1.0% by weight or less, Cu O, 05-0
．． 20% by weight, Mn 0.05% by weight or less, Zn
Examples include 0.10% by weight or less, and 99.00% by weight or more of AI.

As the Al-Cu-Mg system, for example, seal 52017,
SiO, 05-0.20% by weight, FeO, 7% by weight or less, Cu 3.5-4.5% by weight, Mn 0.40-1.
0% by weight, MgO, 40-0.8% by weight, Zn
0.25% by weight or less, CrO, 10% by weight or less, A
1 The remainder is mentioned.

As the Al-Mn system, for example, JIS3003, Si
0.6% by weight or less, Fe0.7% by weight or less, CuO
, 05-0.20% by weight, Mn 1.0-1.5% by weight
, Zn 0.10% by weight or less, and A1 balance.

As the Al-5i system, for example, JIS4032 Si
11.0 to 13.5% by weight, Fe 1.0% by weight or less, C
uO, 50-1.3% by weight, MgO, 8-1.3% by weight, ZnO, 25% by weight or less, CrO, 10
% by weight or less, NiO, 5 to 1.3% by weight, balance A1.

As the Al-Mg system, for example, Jl55086, S
i0.40% by weight or less, FeO, 50% by weight or less,
CuO, 10% by weight or less, Mn 0.20-0.
7% by weight, Mg 3.5-4.5% by weight, ZnO,
25% by weight or less, CrO, 05-0.25% by weight,
Ti is 0.15% by weight or less, and A1 is the balance.

Furthermore, Si 0.50% by weight or less, FeO,
25% by weight or less, CuO, 04-0.20% by weight,
Mn O, 01-1.0% by weight, Mg O, 5-10
Weight%, ZnO, 03 to 0.25% by weight or less, Cr
O, 05-0.50% by weight, Ti or Tr 0.
05 to 0.20% by weight, H, 1.0 cc or less per 1100 grams of A1, the balance being A1.

Further, Si 0.12% by weight or less, Fed
, 15% by weight or less, MnO, 30% by weight or less, M
g O, 5-5.5% by weight, Zn O, 01-1.0
Weight % or less, Cr O, 20 weight % or less, Zr O
, 2.25% by weight or less of O2N, and the balance of AI.

As the Al-Mg-5i system, for example, JIS6063, Si 0.20 to 0.6% by weight, FeO, 35% by weight or less, Cub, 10% by weight or less, Mn 0.10
Weight% or less, Mg0.45-0.9% by weight, ZnO
, 10% by weight or less, Cr O, 10% by weight or less, Ti
0.10% by weight or less, the balance being A1.

As the Al-Zn-Mg system, for example, JT37NO1, Si 0.30% by weight or less, Fe O, 35% by weight or less, Ca O, 20% by weight or less, Ni O, 20~
0.7% by weight, Mg 1.0-2.0% by weight, Zn 4.
0 to 5.0% by weight, CrO, 30% by weight or less, Ti
Examples include: 0.20% by weight or less, ZrO, 25% by weight or less, Vo, 10% by weight or less, and the remainder A1.

In order to select the composition of the aluminum alloy in the present invention, the composition may be appropriately selected by considering the properties depending on the purpose of use, such as mechanical strength, corrosion resistance, workability, heat resistance, dimensional accuracy, etc. When precision machining involves mirror-finishing cutting, etc., the free machinability of the aluminum alloy is improved by coexisting magnesium and/or copper in the aluminum alloy.

In the present invention, the shape of the aluminum support 101 is as follows:
It can be in the shape of a cylindrical or plate-like endless belt with a smooth or uneven surface, and its thickness is determined as appropriate to form a desired electrophotographic light-receiving member.
When flexibility is required as a light-receiving member for electrophotography, it can be made as thin as possible within a range that allows it to function as a support. However, in terms of manufacturing and handling of the support, and from the viewpoint of mechanical strength, it is usually
It is assumed to be 0 μm or more.

When recording an image using coherent light such as a laser beam, irregularities may be provided on the surface of the aluminum support in order to eliminate image defects caused by so-called interference fringe patterns that appear in visible images.

The unevenness provided on the surface of the support is described in Japanese Patent Application Laid-Open No. 60-1681.
56, JP-A-60-178457, JP-A-60-225854, and the like.

Further, as another method for eliminating image defects caused by interference fringe patterns when coherent light such as laser light is used, an uneven 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 smaller than the resolving power required for electrophotographic light-receiving members, and the irregularities are
This is due to multiple spherical trace depressions.

The unevenness formed by the plurality of spherical trace depressions provided on the surface of the support is created by a known method described in JP-A-61-231561.

Lower L layer The lower layer in the present invention is composed of an inorganic material containing small amounts of aluminum atoms (Al), silicon atoms (Si), hydrogen atoms (H), and durability adjusting atoms (CNOc) as constituent elements. , adjust the image quality if necessary.
Mc) may be contained.

Aluminum atoms (A1), silicon atoms (Si), and hydrogen atoms (H) contained in the lower layer are evenly contained in the entire layer region of the lower layer, but their distribution in the layer thickness direction is It has areas with uneven concentration. However, in the in-plane direction parallel to the surface of the support, it is necessary that the content be uniformly distributed and evenly distributed in order to make the properties uniform in the in-plane direction.

Durability adjusting atoms (CNOc) contained in the lower layer
), atoms (Me
) may be contained uniformly in the entire area of the lower layer, or may be contained evenly in the entire area of the lower layer, but unevenly in the layer thickness direction. There may be a portion where the content is distributed. However, in any case, it is necessary that the content be uniformly distributed in the in-plane direction parallel to the surface of the support in order to make the properties uniform in the in-plane direction.

Furthermore, in one of the preferred embodiments, aluminum atoms (A1) and silicon atoms (
The distribution state of aluminum atoms (Si) and hydrogen atoms (H) is such that aluminum atoms (AI), silicon atoms (Si), and hydrogen atoms (H) are continuously and evenly distributed in the entire layer region, and the aluminum atoms (At) are distributed uniformly throughout the layer. The distribution concentration in the thickness direction decreases from the support side toward the upper layer, and silicon atoms (Si
), the distribution concentration of hydrogen atoms (H) in the layer thickness direction increases from the support side toward the upper layer, so the affinity between the aluminum support and the lower layer and between the lower layer and the upper layer is improved. Excellent.

In the electrophotographic light-receiving member of the present invention, as described above, aluminum atoms (AI) contained in the lower layer,
The distribution state of silicon atoms (S i ) and hydrogen atoms (H) is as described above in the layer thickness direction, and is uniformly distributed in the in-plane direction parallel to the surface of the support. is desirable.

3 to 8 show aluminum atoms (Al
), a durability adjusting atom (CNoc), and an image quality adjusting atom (M, ) contained as necessary, typical examples of the distribution state in the layer thickness direction are shown.

In Figures 3 to 8, the horizontal axis is the aluminum atom (
AI) (hereinafter abbreviated as “atomic (Al)J”), durability adjusting atom (CNOc) (hereinafter “atomic (CNOC)
)J), atom (Mc) that adjusts image quality (hereinafter abbreviated as "atomic (Me)J", atom (AI) and atom (CNO)
c) and atoms (M,) are collectively abbreviated as ``atoms (AC)J.However, atoms (AI), atoms (CNOc), and atoms (M
The distribution state of C) in the layer thickness direction may be the same or different. The vertical axis indicates the layer thickness of the lower layer, and t! l indicates the position of the end face of the lower layer on the support side, and ta indicates the position of the end face of the lower layer on the upper layer side. That is, the lower layer containing atoms (AC) is formed from the t side toward the 11 side.

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

In the example shown in FIG. 3, the distribution concentration C of the contained atoms (AC) is from position t to position ti+, which is the concentration C81.
The distribution state is such that the concentration CHI decreases in a linear function from the position tal to the position t7, and reaches the concentration C82 at the position tT.

In the example shown in FIG. 4, the distribution concentration C of the contained atoms (AC) is the concentration C4 from position ta to position 11.
The concentration C decreases linearly from 1 at the position tT.
A distribution state of 4□ is formed.

In the example shown in FIG.
A distribution state is formed in which the concentration gradually and continuously decreases from t to a concentration Cs at position t7.

In the example shown in FIG. 6, the distribution concentration C of the contained atoms (AC) is from position t to position ta+, which is the concentration C61.
From position ts+ to position 1, the concentration decreases in a linear function from C6□, forming a distribution state in which the concentration reaches C68 at position 11.

In the example shown in FIG. 7, the distribution concentration C of the contained atoms (AC) takes a constant value of concentration C7+ from position t to position t7+, and gradually increases from concentration C0 to position t7 from position tt+. The concentration decreases continuously to form a distribution state in which the concentration becomes C7m at the position 1T.

In the example shown in FIG.
The concentration gradually and continuously decreases from 0 to 0 at position tT.
．． A distribution state of 2 is formed.

As described above with reference to FIGS. 3 to 8, some typical examples of the distribution state of atoms (A1) contained in the lower layer in the layer thickness direction, in the present invention, on the support side,
A portion containing silicon atoms (Si) and hydrogen atoms (H) and having a high distribution concentration C of atoms (A1), where the distribution concentration C is considerably lower at the interface ta than on the support side. A preferred example is formed when the

In this case, the maximum value CmaX of the distribution concentration of atoms (A1) is preferably 10 at% or more, more preferably 30 at%
As mentioned above, it is desirable to form layers so that the distribution state is optimally 50 atomic % or more.

In the present invention, the content of atoms (A1) contained in the lower layer is determined as desired so as to effectively achieve the object of the present invention, but preferably exceeds 5 at% and 95%. It is desirable that the content be atomic % or less, more preferably 10 to 90 atomic %, most preferably 20 to 80 atomic %.

9 to 16 show silicon atoms (Si) contained in the lower layer of the electrophotographic light receiving member of the present invention.
), hydrogen atoms (H) atoms (CN Oc), and atoms contained as necessary (Me ) in the layer thickness direction.

In FIGS. 9 to 16, the horizontal axis represents silicon atoms (S
i) , hydrogen atom (H), atom (CNOc), atom (
MC), (Hereinafter, these will be collectively abbreviated as "atoms (SHC)J."However, silicon atoms (S i) and hydrogen atoms (H
), the distribution state of atoms (CNOc), and atoms (MC, ) in the layer thickness direction may be the same or different), the vertical axis indicates the layer thickness of the lower layer, and t , indicates the position of the end face of the lower layer on the support body side, and t7 indicates the position of the end face of the lower layer on the upper layer side. That is, the lower layer containing atoms (SHC) is 1. The layers are formed from the side toward the t-layer side.

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

In the example shown in FIG. 9, the distribution concentration C of the contained atoms (SHC) increases numerically from the concentration CII for one hour from the position t to the position t, and from the position to+ to the position t7. Up to this point, a distribution state is formed that takes a constant value of concentration C92.

In the example shown in FIG. 10, the atoms contained (SHC)
The distribution concentration C of is the concentration C1 from position t to position t7.
A distribution state is formed in which the concentration increases linearly from 1° to a concentration C1° at position ta.

In the example shown in FIG. 11, the atoms contained (SHC)
The distributed concentration C gradually and continuously increases from the concentration C311 from the position ta to the position t7, and forms a distribution state in which the concentration C112 is reached at the position t7.

In the example shown in FIG. 12, the atoms contained (SHC)
The distribution concentration C increases numerically from the concentration C1□ for one hour until it reaches the position t121, and becomes the concentration C122 at the position t121, and from the position t2゜1 to the position ta, the concentration becomes a constant concentration C1□. It forms a distribution state that takes on values.

In the example shown in FIG. 13, the contained atoms (SHC)
The distribution concentration C gradually and continuously increases from the position t to the position tIl+ until the concentration C gradually and continuously increases from the position tIll+ to the position tIll+.
The density becomes C1□ at 131, and a distribution state is formed in which the density takes a constant value of C+ss from position t131 to position ta.

In the example shown in FIG. 14, the contained atoms (SHC)
The distribution concentration C gradually and continuously increases from the concentration C841 from the position t to the position 11, and forms a distribution state in which the concentration C142 is reached at the position 11.

In the example shown in FIG. 15, the contained atoms (SHC)
The distribution concentration C is substantially zero from position t8 to position t151 (substantially zero here means the case where the amount is less than the detection limit, and the meaning of "substantially zero" hereinafter is also the same). The concentration CII1 gradually increases from 161 to 161.
From position t161 to position t7, the concentration CI
A distribution state is formed that takes a constant value I2.

In the example shown in FIG. 16, the contained atoms (SHC)
The distribution concentration C gradually increases from substantially zero from position t to position 11 until the concentration C18 at position 11.
, a distribution state is formed.

As described above with reference to FIGS. 9 to 16, some typical examples of the distribution state of silicon atoms (Si) and hydrogen atoms (H) contained in the lower layer in the layer thickness direction, in the present invention, is an aluminum atom (AI) on the support side
and has a portion with a low distribution concentration C of silicon atoms (Si) and hydrogen atoms (H), and has a portion where the distribution concentration C is considerably higher than that on the support side at the interface tT. (S i ), a preferable example is formed when the distribution state of hydrogen atoms (H) is provided in the lower layer. In this case, silicon atoms (Si),
The maximum distribution concentration Cmax of the sum of hydrogen atoms (H) is preferably 10 atomic % or more, more preferably 30 atomic % or more, and optimally 50 atomic % or more. Preferably, it is layered.

In the present invention, silicon atoms (
The content of Si) is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 5 to 95 atomic %, more preferably 10 to 90 atomic %.
The optimum content is preferably 20 to 80 atomic %.

In the present invention, hydrogen atoms (H) contained in the lower layer
The content is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 0.
01 to 70 at%, more preferably 0.1 to 50 at%
The optimum content is preferably 1 to 40 atomic %.

As the atom (CNOc) for adjusting the durability, a carbon atom (C), a nitrogen atom (N), and an oxygen atom (0) are used. In the present invention, by containing carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) as atoms (CNOc) for adjusting durability in the lower layer, the aluminum-based support is and/or the effect of improving charge injection between the upper layer and the upper layer.
Alternatively, the effect of improving running properties in the lower layer and/or the effect of improving the adhesion between the aluminum support and the upper layer can be obtained. Furthermore, the effect of controlling the forbidden band width can also be obtained in a layer region in which the content of aluminum atoms (AI) is small in the lower layer. The content of durability adjusting atoms (CNOC) contained in the lower layer is preferably 1 x 101 to 5 x 10' atoms 1) I) m%
More preferably 5 x 10' to 4 x 108 atomic ppm.

Optimally, a range of 1X10'' to 3X10'' atoms ppm is desirable.

Atoms (M
c) is an atom belonging to group Ⅰ of the periodic table (hereinafter abbreviated as ``group Ⅰ atom''), excluding nitrogen atom (N) (atom belonging to group V of the periodic table (hereinafter abbreviated as ``group V atom''). (abbreviated as atom)
, atoms belonging to group Vl of the periodic table (hereinafter abbreviated as "group VI atoms") excluding oxygen atom (0) are used. Specifically, the Group Ⅰ atoms include B (boron), AI (aluminum), Ga (gallium), and In (indium).

Examples include TI (thallium), and B, AI, and Ga are particularly preferred. Specifically, the Group V atoms include P (phosphorus), A
s (arsenic), Sb (antimony).

Examples include Bi (bismuth), and P and As are particularly preferred. Specifically, the Group VI atoms include S (sulfur),
Se (selenium), Te (tellurium).

Examples include Po (polonium), and S and Se are particularly preferred. In the present invention, atoms (
M,) as a group II atom or a group V atom or a group VI atom
By containing the group atoms, it is possible to mainly obtain 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 migration property in the lower layer. Furthermore, it is possible to obtain the effect of controlling the conductivity type and/or conductivity in a layer region in which the content of aluminum atoms (AI) is low in the lower layer. The content of atoms (Mc) that adjusts the image quality contained in the lower layer is preferably lXl0-"~5
X10' atoms ppm, more preferably lXl0-''~l
Xl0' atoms ppm, optimally lX10''~5×10
It is desirable that the content be s atoms ppm.

In the present invention, the lower layer composed of Al5iH is formed, for example, by the same vacuum deposition film forming method as the upper layer described later, with numerical conditions of film forming parameters set appropriately so as to obtain desired characteristics. Ru. Specifically, for example, glow discharge method (alternating current discharge CVD such as low frequency CVD, high frequency CVD or microwave CVD, or direct current discharge CVD), ECR-CVD method, sputtering method,
It can be formed by a number of thin film deposition methods such as a vacuum evaporation method, an ion blating method, and a photo-CVD method.

These thin film deposition methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be produced. It is relatively easy to control the conditions for manufacturing electrophotographic light-receiving members with specific characteristics, and hydrogen atoms can be easily introduced in addition to aluminum atoms and silicon atoms. A discharge method, a sputtering method, and an ion blating method are suitable.

These methods may also be used in combination within the same equipment area. For example, by glow discharge method, Al5i
In order to form the lower layer composed of H, basically, a raw material gas for A1 supply that can supply aluminum atoms (A1), a Si supply gas that can supply silicon atoms (Si), an H supplying gas capable of supplying hydrogen atoms (H);
CNO, which can supply atoms that improve durability (CNOc);
M capable of supplying supply gas and, if necessary, adjusting image quality (M,); A supply gas is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber, thereby depositing Al5iH onto the surface of a predetermined support that has been placed in a predetermined position. What is necessary is to form a layer consisting of.

When forming by sputtering method, for example, Ar,
A target made of A1 in an atmosphere of an inert gas such as He or a mixed gas based on these gases,
Hydrogen atoms (H
) and a CN0c supplying gas capable of supplying atoms (CNO, ) for adjusting durability;
Introducing a Mc supply gas capable of supplying atoms (Mc) for adjusting image quality as necessary into a deposition chamber for sputtering,
Furthermore, if necessary, a source gas for A1 supply that can supply aluminum atoms (A1) and/or a Si supply gas that can supply silicon atoms (Si) are introduced into the deposition chamber for sputtering to obtain the desired This is accomplished by creating a gas plasma atmosphere.

In the case of the ion blating method, for example, aluminum and polycrystalline silicon or single crystal silicon are housed in an evaporation board as evaporation sources, and the evaporation sources are heated by a resistance heating method or an electron beam method (EB method). This can be carried out in the same manner as in the sputtering method, except for heating and evaporating and passing the flying evaporated material through a desired gas plasma atmosphere.

In the present invention, when forming the lower layer, aluminum atoms (A1) and silicon atoms (Si) contained in the layer are
, hydrogen atom (H) atom that adjusts durability (CNOc)
, an atom (Me) that adjusts the image quality if necessary
To form a layer having a desired depth profile by changing the distribution concentration C of atoms (hereinafter collectively referred to as "atomic (ASH) J") in the layer thickness direction, In the case of the glow discharge method, this is accomplished by introducing a raw material gas for supplying atoms (ASH) whose distribution concentration is to be changed into the deposition chamber while changing its gas flow rate appropriately according to a desired rate of change curve. Ru.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system is changed as appropriate by any commonly used method such as manually or by an externally driven motor.

When forming by sputtering method, atoms (A S
) In order to change the distribution concentration C of I) in the layer thickness direction to form a layer having a desired depth profile, first, as in the case of the glow discharge method, This is accomplished by using a raw material for supplying atoms (A S H) in a gaseous state, changing the gas flow rate appropriately according to a desired rate of change curve, and introducing the gas into the deposition chamber.

Second, the target for sputtering, for example, AI
If a target containing a mixture of AI and Si is used, this can be done by changing the mixing ratio of AI and Si in advance in the layer thickness direction of the target.

Examples of substances that can be used as the raw material gas for supplying A1 used in the present invention include AlCl5. AlBr5゜AIl,,
Al (CH,), CI, AI (CH,),.

AI (OCH3)s, AI (CIHs)s, AI(
OCz Ha) s, AI (i-C4He)
s, AI (i-CsH?) s, AI (C3H5)
1, AI(QC4H,), etc. can be cited as examples of those that can be effectively used. Further, these raw material gases for supplying Al may be diluted with gases such as H2, He, Ar, Ne, etc. as necessary.

Substances that can be used as the raw material gas for supplying St used in the present invention include S i H4 and S i2 Ha.

Silicon hydride (silanes) in a gaseous state such as S is Hs r S ia 1 (+O) or that can be gasified is cited as one that can be effectively used, and it is also easy to handle during layer creation work, Si supply efficiency SiH4,
5i2Hs is preferred. In addition, these raw material gases for Si supply may be converted into H2, He, etc. as necessary.
, Ar, Ne, etc. may be used after diluting with gas.

Substances that can be the raw material gas for hydrogen supply used in the present invention include H2+, 5iHa, 5i2H
Silicon hydride (silanes) such as s, 5isHs, 5i4)(+.) can be mentioned as those that can be effectively used.

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

To structurally introduce atoms (CNOc) that adjust durability into the lower layer, such as carbon atoms (C), nitrogen atoms (N), or oxygen atoms (0), carbon atoms (CNOc) are added during layer formation. ) A raw material for introduction, a raw material for nitrogen atom (N) introduction, or a raw material for oxygen atom (0) introduction is introduced in a gaseous state into the deposition chamber together with other raw materials for forming the lower layer. Just do it. Materials that can be used as raw material for introducing carbon atoms (C), raw materials for introducing nitrogen atoms (N), or raw materials for introducing oxygen atoms (0) are those that are in a gas state at room temperature and pressure, or at least in a layered state. It is desirable to use a material that can be easily gasified under the formation conditions.

Starting materials that can be effectively used as raw material gases for introducing carbon atoms (C) include saturated hydrocarbons containing C and H as constituent atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, and saturated hydrocarbons having 2 to 4 carbon atoms.
Examples include ethylene hydrocarbons, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, the saturated hydrocarbon is methane (CH,)
, ethane (C,H,), propane (C.

Hs), n-butane (n-Ca H+o) rpentane (Cs H+-), and ethylene hydrocarbons include ethylene (C, H,) and propylene (C, H,).

Butene-1 (C,H,), Butene-2 (C,H,).

Isobutylene (C,H#), Pentene (C,H,.).

Acetylene (C.

H2), methylacetylene (C,H,), butyne (C,
H, ), etc.

As a raw material gas containing Si, C, and H as constituent atoms, S
t (CHs) a, S i (Ca Hs
) Examples include alkyl silicides such as a.

In addition to this, in addition to introducing carbon atoms (C), halogen atoms (X) can also be introduced, so CF, CC1,
, CH, cFs, and other halogenated carbon gases.

Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms (N) include nitrogen (N, ), which has N as a constituent atom, or has N and H as constituent atoms,
Ammonia (NHS), hydrazine (H= N N H
x), hydrogen azide (HN, ).

Gaseous or gasifiable nitrogen such as ammonium azide (NH,N, ), nitrogen compounds such as nitrides and azides may be mentioned. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (F, N), nitrogen tetrafluoride (F4N
, ), etc. can be mentioned.

Starting materials that can be effectively used as raw material gases for introducing oxygen atoms (0) include, for example, oxygen (0,), ozone (0,), and nitrogen oxide (No).

Nitrogen dioxide (N　O, ), -nitrogen dioxide (N,O).

Nitrogen sesquioxide (N, O,), trinitrogen tetraoxide (N 204
), nitrogen sesquioxide (N, O, ), nitrogen dioxide (NOx)
, silicon atom (Si), oxygen atom (0) and hydrogen atom (
For example, disiloxane (Hs
5iO8iHs)*) Disiloxane (Hs 5iO
Examples include lower siloxanes such as 8iHz 03iH*).

In the lower layer, there is an atom (Mc) that adjusts the image quality, for example No.
In order to structurally introduce a group atom, a group V atom, or a group Vl atom, when forming a layer, a raw material for introducing a group I atom, a raw material for introducing a group V atom, or a group VI atom is used. The raw material for introducing atoms may be introduced in a gaseous state into the deposition chamber together with other raw materials for forming the lower layer. Raw material for introduction of Group Ⅰ atoms or Group V
As raw materials for introducing group atoms or materials that can be used as raw materials for introducing group VI atoms, those that are gaseous at normal temperature and pressure, or at least can be easily gasified under layer-forming conditions, are used. is desirable.

Specifically, as raw materials for introducing such Group Ⅰ atoms, B, H, etc. are used for introducing boron atoms.

B.H. , Be Hs, B=Hll, B6Hr.

Boron hydride such as +B8Hli B s H14, BF,
, BCl, , BBr, and other boron halides. In addition, AI CIs, GaCls, G
a (CH3)5. InC1a, TlCl5, etc. can also be mentioned.

In the present invention, the raw materials for introducing Group V atoms that are effectively used for introducing phosphorus atoms are PH,
Hydrogen north neighbor of P, H, etc., PH4I r P F 3,
P F B I P Cl s + P C ] a ,
Examples include halogen ratios such as PBrs, PBra, Pis. In addition, AsHs, AsF5, AsC
l3, AsBr5, AsF5.5bHs, SbF
a , S b F s + S b C1s + S
b CI s + B IH,, B1C1m, Bi
Brx and the like can also be mentioned as effective starting materials for introducing Group V atoms.

Hydrogen sulfide (H
,S) ,SF, ,SF, ,So, ,S
o.

F,,CO3,C8,,CH,5HC2H,SH,C4
Mention may be made of substances in a gaseous state or which can be gasified, such as H, S, (CHI)2S(C,Hs)2S. Other SC
HI, S e Fs, (CHs)iSe,
(C2Hs)i Se, TeHz, TeFs *(C
Examples include substances in a gaseous state or which can be gasified, such as Hs )2 Te, ((l Hs)i Te, etc.).

Further, the raw material for introducing atoms (Mc) to control the image quality may be Hz, He, Ar, etc. as necessary.

It may be used after being diluted with a gas such as Ne.

The thickness of the lower layer in the present invention is 0.003 mm from the viewpoint of obtaining desired electrophotographic properties and economical effects.
~5 μm, preferably 0.01-1 μm, optimally 0.
It is desirable that the thickness be 0.05 to 0.5 μm.

In the present invention, the end face of the lower layer with the aluminum support is a region where the content of aluminum atoms in the lower layer is 95% or less of the content of aluminum atoms in the aluminum support. This is because in a composition region where the content of aluminum (A1) atoms exceeds 95% of the content of aluminum atoms (A1) in the aluminum-based support, its function is almost solely as a support. . Furthermore, the end face of the lower layer with the upper layer is a region where the content of aluminum atoms in the lower layer exceeds 5%. This means that in the composition range where the content of aluminum atoms (A1) is 5% or less,
This is because its function is almost only that of an upper layer.

In order to achieve the object of the present invention and to form a lower layer made of Al5iH having stable properties, it is necessary to appropriately set the gas pressure in the deposition chamber and the temperature of the support as desired.

The optimum range of gas pressure in the deposition chamber is selected according to the layer design, but normally it is lXl0-'~10Torr
, preferably I x 10-' to 3 Torr.

Optimally, it is preferable to set it to lXl0-' to ITorr.

The support temperature (Ts) is suitably selected in an optimal range according to the layer design, but it is usually desirably 50 to 600°C, preferably 100 to 400°C.

In the present invention, when the lower layer made of Al5iH is created by the glow discharge method, the optimal range of discharge power supplied into the deposition chamber is selected as appropriate according to the layer design, but in normal cases, the discharge power is 5X10-' to 10W/crrr. , preferably 5 X 10-' to 5 W/crd, optimally I
It is desirable to set it as 10-'' to 2 x 10-'W/c rrr.

In the present invention, the above-mentioned desirable numerical ranges for the gas pressure in the deposition chamber, the support temperature, and the discharge power supplied to the deposition chamber for creating the lower layer include the above-mentioned ranges, but these layer creation factors are usually The upper layer in the present invention is not determined independently and separately, but is based on mutual and organic relationship to form the lower layer with desired properties. -3i (H.

X) and has desired photoconductive properties.

In the present invention, carbon atoms (C) and/or nitrogen atoms (N
) and/or oxygen atoms (0), and may also contain atoms (M) that control conductivity if necessary, but neither germanium atoms (Ge) nor tin atoms (S n) are substantially present. It is not contained in the target. However, in other layer regions of the upper layer, atoms controlling conductivity (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge), tin atoms ( It may contain at least one of the following. Particularly in the layer region near the free surface of the upper layer, it is preferable to contain at least one of carbon atoms (C), nitrogen atoms (N), and oxygen atoms (0).

The upper layer has a small amount of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) contained in the layer region in contact with the lower layer and/or conductivity contained as necessary. The atoms (M) that control the may be uniformly distributed throughout the layer region, or may be uniformly contained within the layer region but distributed non-uniformly in the layer thickness direction. There may be a portion containing it in such a state.

However, in any case, it is necessary that the content be uniformly distributed and evenly distributed in the in-plane direction parallel to the surface of the support in order to make the properties uniform in the in-plane direction.

Atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge
), tin atom (S n), the conductivity controlling atom (M), carbon atom (C), nitrogen atom (N), oxygen atom (0), germanium atom ( Ge) Tin atoms (S n) may be distributed uniformly in the layer region, or they may be contained evenly in the layer region but non-uniformly in the layer thickness direction. However, in any case, in the in-plane direction parallel to the surface of the support, it is important that the content is uniformly distributed. This is also necessary from the point of view of making the characteristics uniform in the in-plane direction.

In addition, atoms (M) that control conductivity (hereinafter referred to as "atoms (M)"
(abbreviated as “layer region (M)”) (hereinafter referred to as “layer region (M)
), and at least a lower layer of the upper layer containing a carbon atom (C) and/or a nitrogen atom (N) and/or an oxygen atom (0) (hereinafter abbreviated as "atom (CNO) J"). Contacting layer region (hereinafter referred to as “layer region (CNO,) J
) may be substantially the same layer region, or may share at least a part of the surface side of the layer region (CNO, ).

In addition, a layer region (hereinafter abbreviated as "layer region (GS) J") containing germanium atoms (Ge) and/or tin atoms (Sn) (hereinafter abbreviated as "atomic (GS) J") is a layer region (CNO , ') may share part of the surface side.

In addition, a layer region containing atoms (CNO) other than the layer region (CN Oa) (hereinafter abbreviated as "layer region (CNOT)",
In addition, the layer region (CNO,) and the layer region (CNoT) are collectively referred to as [layer region (CNO) j], and the layer region (M)
The layer regions (GS) may be substantially the same layer region, may share at least a part of each layer region, or may substantially share each layer region. It doesn't have to be.

17 to 36 show typical examples of the distribution state of atoms (M) contained in the layer region (M) in the layer thickness direction in the upper layer of the electrophotographic light-receiving member of the present invention. A typical example of the distribution state of atoms (CNO) contained in the layer region (CNO) in the layer thickness direction, atoms contained in the layer region (GS) (
GS) shows a typical example of the distribution state in the layer thickness direction. (Hereinafter, the layer region (M), layer region (CNO), and layer region (GS) will be referred to as "layer region (Y)" and atoms (
M), atom (CNO), and atom (GS) are represented by "atom (Y)". Therefore, although FIGS. 17 to 36 show typical examples of the distribution state of atoms (Y) contained in the layer region (Y) in the layer thickness direction, as described above, the layer region ( M) When the layer region (CNO) and the layer region (GS) are substantially the same layer region, the layer region (Y) is singularly contained in the upper layer and is not substantially the same layer region. In some cases, a plurality of layer regions (Y) are arranged in the upper layer).

17 to 36, the horizontal axis shows the distribution concentration C of atoms (Y), the vertical axis shows the layer thickness of the layer region (Y), and t is the end face of the layer region (Y) on the lower layer side. , and tT indicates the position of the end face of the layer region (Y) on the free surface side. That is, the layer region (Y) containing atoms (Y) is formed as a layer from the ta side toward the t7 side.

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

In the example shown in FIG. 17, the distribution concentration C of the contained atoms (Y) is the concentration C1 from position t to position t7.
7, the concentration increases gradually and continuously, forming a distribution state in which the concentration C172 is reached at position ta.

In the example shown in FIG. 18, the distribution concentration C of the contained atoms (Y) increases numerically from the concentration CIII for one hour from the position ta to the position t181, and becomes the concentration CI8□ at the position t+s+, From position t181 to position tT, a distribution state is formed in which the concentration takes a constant value of C+ss.

In the example shown in FIG. 19, the distribution concentration C of the contained atoms (Y) has a constant value of concentration CIII from position tll to position tIII, and from position t191 to position t192. Gradually and continuously increasing from C1,1 to position t89. The concentration becomes C1, 2 at the position tI92 to the position t7, forming a distribution state in which the concentration takes a constant value C+os.

In the example shown in FIG. 20, the distribution concentration C of the contained atoms (Y) is from position t to position t2°.

The concentration becomes a constant value of C2゜1 until reaching the position t2.
゜, position t,. The density becomes a constant value of C8°2 until reaching the position t. From 2 to position tT, the concentration is C2.
It forms a distribution state that takes a certain value.

In the example shown in FIG. 21, the distribution concentration C of the contained atoms (Y) is at position 1. The density is off until position t7.
A distribution state is formed such that the constant value l + is reached.

In the example shown in FIG. 22, the distribution concentration C of the contained atoms (Y) is from position t to position t, and up to 21 the concentration C2
A distribution state is formed in which the concentration takes a constant value m+ and gradually and continuously decreases from the concentration C222 from the position t221 to the position ta, and reaches the concentration C2ff8 at the position 11.

In the example shown in FIG. 23, the distribution concentration C of the contained atoms (Y) is the concentration C0 from position t8 to position 11.
, gradually and continuously decreases, forming a distribution state in which the concentration reaches C232 at position t7.

In the example shown in FIG. 24, the distribution concentration C of the contained atoms (Y) is from position t8 to position t, and from position t to position 41 is the concentration C3.
4, and gradually and continuously decreases from the concentration C24 from the position t and 41 to the position t7, and the distribution concentration C becomes substantially zero at the position ta (here, it becomes substantially zero). is a case where the amount is less than the detection limit, and the meaning of "substantially zero" hereinafter is also the same).

In the example shown in FIG. 25, the distribution concentration C of the contained atoms (Y) is the concentration C2 from position t to position t7.
A distribution state is formed in which the distribution concentration C gradually and continuously decreases from 111 to become substantially zero at position 11.

In the example shown in FIG. 26, the distribution concentration C of the contained atoms (Y) is from position t to position t□.

From position t1,1, the concentration Csst is a constant value, and from position t1,1 to position ta, the concentration decreases in a -order function from C16, forming a distribution state in which the concentration becomes C1 at position t7. There is.

In the example shown in FIG. 27, the distribution concentration C of the contained atoms (Y) is the concentration C2 from position t8 to position 11.
, 1, forming a distribution state in which the distribution concentration C decreases linearly from 1 to substantially zero at the position t7.

In the example shown in FIG. 28, the distribution concentration C of the contained atoms (Y) is from position t to position t28°, which is the concentration C2.
, 1, and decreases in a linear function from the concentration C2,l from position t281 to position t7.
, a distribution state is formed such that the concentration C2, .

In the example shown in FIG. 29, the distribution concentration C of the contained atoms (Y) is the concentration C2 from position t to position t7.
A distribution state is formed in which the concentration gradually and continuously decreases from 11 to a concentration C29 at position tT.

In the example shown in FIG. 30, the distribution concentration C of the contained atoms (Y) is from the position t to the position t8°1, which is the concentration C3.
It takes a constant value of 1°, and from position tsat to position t7, the concentration decreases linearly from C1°2 to position tT.
A distribution state is formed such that the concentration is C1°.

In the example shown in FIG. 31, the distribution concentration C of the contained atoms (Y) increases gradually and continuously from the concentration C811 from the position t to the position tIll, and at the position t1,1 the concentration C812 increases. Thus, a distribution state is formed in which the concentration takes a constant value C318 from position t3□ to position ta.

In the example shown in FIG. 32, the distribution concentration C of the contained atoms (Y) is at position 1. The concentration CI until the position ta is reached.
A distribution state is formed in which the concentration increases gradually and continuously from 21 to reach the concentration Csxx at the position tr.

In the example shown in FIG. 33, the distribution concentration C of the contained atoms (Y) is substantially zero from position t8 to position tsst (here, substantially zero means that the concentration is below the detection limit). (the meaning of "substantially zero" hereinafter is also the same), the concentration gradually increases to C1 at position tIll, and from position taal- to position 11, the concentration C1.
8,! A distribution state is formed that takes a certain value.

In the example shown in FIG. 34, the distribution concentration C of the contained atoms (Y) gradually increases from substantially zero from position t8 to position t7, and reaches the concentration C341 at position ta. It forms a distribution state.

In the example shown in FIG. 35, the distribution concentration C of the contained atoms (Y) increases linearly from the concentration c set from position t to position t8,1, and from position t8,1 A distribution state is formed in which the concentration takes a constant value of C3° up to position ta.

In the example shown in FIG. 36, the distribution concentration C of the contained atoms (Y) is from position t to position 11, the concentration C16,
The concentration c at position ta increases exponentially from
6. The distribution state is formed as follows.

Examples of the atoms (M) that control the conductivity include so-called impurities in the semiconductor field. (abbreviated as "group atom") or n
Periodic table V excluding the nitrogen atom (N) which gives type conductivity properties
(hereinafter abbreviated as "Group V atoms") and atoms belonging to Group ■ of the periodic table, excluding oxygen atoms (0) (hereinafter abbreviated as "Group V atoms")
Hereinafter abbreviated as "Group I atoms") will be used. Specifically, the Group Ⅰ atoms include B (boron), A1 (aluminum), Ga (gallium), In (indium), 'rt
(thallium), etc., especially B, A1. Ga is preferred. Specifically, the Group V atoms include P (phosphorus),
Examples include As (arsenic), Sb (antimony), Bi (bismuth), and P and As are particularly preferred. Specifically, the Group Ⅰ atoms include S (sulfur) and Se (selenium).
, Te (tellurium), Po (polonium), etc., with S and Se being particularly suitable. In the present invention, the layer region (M
) by containing a group Ⅰ atom, a group V atom, or a group ① atom as an atom (M) that controls conductivity, the effect of mainly controlling the conductivity type and/or conductivity and/or the layer region ( M) and the layer area of the upper layer (M)
It is possible to obtain the effect of improving the charge injection property between layer regions other than the above. The content of atoms (M) that control conductivity contained in the layer region (M) is preferably 1×10
-” to 5×10′ atoms I)m%, preferably 1×
10 bows ~ I x 10' atoms pI) m N optimally 1
xlO-' to 5X10'' atoms ppm. Particularly in the layer region (M), carbon atoms (C), which will be described later,
and/or when the content of nitrogen atoms (N) and/or oxygen atoms (0) is less than lXl0'' atoms ppm,
Atoms (M) that control conductivity contained in the layer region (M)
The content is preferably 1xlO-” to 1xlO
"It is preferable to set it as atomic ppm, and carbon atom (C) and/or nitrogen atom (N) and/or oxygen atom (0
) exceeds 1X10'' atomic ppm, the content of the atom (M) that controls conductivity is preferably 1X10-' to 5X10' atomic ppm.

In the present invention, carbon atoms (C) are added to the layer region (CNO).
and/or by containing nitrogen atoms (N) and/or oxygen atoms (0), mainly to increase the dark resistance and/or hardness and/or to control the spectral sensitivity and/or to control the layer region (CNO) and the upper part. The layer area of the layer (C
It is possible to obtain the effect of improving the adhesion between layer regions other than NO). The content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) contained in the layer region (CNO) is preferably 1 to 9×
1011 atom pI) m%, preferably lXl0'~5
X10' atomic ppm, optimally 1 x 102 to 3 x 101
' It is preferable to set it as atomic ppm. In particular, when aiming for high dark resistance and/or high hardness, preferably lXl
It is desirable that the range is 0" to 9 x 108 atomic ppm, and when controlling the spectral sensitivity, it is preferably lXl0" to 5
It is preferable that X10' atoms ppm.

In the present invention, by containing germanium atoms (Ge) and/or tin atoms (Sn) in the layer region (GS), it is possible to mainly control the spectral sensitivity, particularly when using a semiconductor laser or the like as an image exposure source of an electrophotographic device. It is possible to obtain the effect of improving long wavelength light sensitivity when using long wavelength light. Germanium atoms (G
The content of e) and/or tin atoms (Sn) is preferably 1 to 9.5 x 10' atomic ppm, more preferably 1 x 102 to 8 x 10 I' atomic ppm.

Optimally, it is desired to be between 5X10" and 7X10' atomic ppm.

Further, hydrogen atoms (H) contained in the upper layer in the present invention
And/or halogen atoms (X) can compensate for dangling bonds of silicon atoms and improve layer quality. Hydrogen atoms (H) contained in the upper layer, or hydrogen atoms (
The total content of H) and halogen atoms (X) is preferably l
The content of halogen atoms (X) is preferably 1 to 4×1
It is desirable that the content be 01' atomic ppm. In particular, the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) described above in the upper layer is 3.
When X10' atomic ppm or less, the content of hydrogen atoms (H) or the sum of hydrogen atoms (H) and halogen atoms (X) is desirably set to IX10'' to 4X10' atomic ppm.

Furthermore, if the upper layer is composed of polycrystalline material,
The content of hydrogen atoms (H) or the sum of hydrogen atoms (H) and halogen atoms (X) contained in the upper layer is preferably ixio" to 2X10' atomic ppm. When it is desirably made of an amorphous material, it is preferably lXl0' to 7 x 106 atomic ppm.

In the present invention, the upper layer composed of No n-3i (H, Ting method, HRCV
D method and FOCVD method are preferred. These methods may be used in combination within the same device system.

For example, Non-8i (H
, X), basically a Si supply gas capable of supplying silicon atoms (Si);
N supply gas capable of supplying hydrogen atoms (H) and/or X supply gas capable of supplying halogen atoms (X), and N supply capable of supplying atoms (M) for controlling conductivity as necessary C that can supply gas and/or carbon atoms (C) for
Supply gas and/or N supply gas capable of supplying nitrogen atoms (N) and/or C supply gas capable of supplying oxygen atoms (0) and/or germanium atoms (Ge)
Ge supply gas and/or tin atoms (
A Sn supplying gas capable of supplying Sn) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber. A layer made of Non-3i (H,X) may be formed on the surface of the support on which a lower layer has been formed in advance.

To form the upper layer composed of Non-3i (H, N supply gas capable of supplying atoms (M) and/or C supply gas capable of supplying carbon atoms (C) and/or N supply gas capable of supplying nitrogen atoms (N) and/or oxygen atoms C supply gas capable of supplying (0) and/or Ge supply gas capable of supplying germanium atoms (Ge) and/or tin atoms (S n
) is introduced at a desired gas pressure into the activation space provided at the front stage of the deposition chamber, the interior of which can be reduced in pressure, separately or together as required. Active species (A) are generated by generating glow discharge or heating in the activation space, and hydrogen atoms (H
) and/or halogen atoms (
A halogen supplying gas capable of supplying X) is similarly introduced into another activation space to generate active species (B), and active species (A)
and active species (B) were separately introduced into the deposition chamber, and the non-8t (H,
A layer consisting of X) may be formed.

To form the upper layer composed of Non-3i (H,
) and/or an N supply gas capable of supplying atoms (M) that control conductivity as necessary.
or C supply gas capable of supplying carbon atoms (C) and/or N supply gas capable of supplying nitrogen atoms (N) and/or C supply gas capable of supplying oxygen atoms (0) and/or germanium G that can supply atoms (Ge)
Introducing e supply gas and/or Sn supply gas capable of supplying tin atoms (Sn), separately or together as necessary, at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure. Furthermore, halogen (X) gas is introduced into the deposition chamber at a desired gas pressure separately from the supply gas, and these gases are caused to undergo a chemical reaction within the deposition chamber, so that the halogen (X) gas is pre-installed at a predetermined position. A layer made of Non-3i (H,

To form the upper layer composed of Non-8i (H,
It may be formed by a known method described in publications and the like.

In the present invention, when forming the upper layer, atoms (M) that control conductivity contained in the layer, carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge
), tin atom (Sn) (hereinafter these will be collectively referred to as “atomic (
A desired distribution state (depth
In the case of the glow discharge method, HRCVD method, and FOCVD method, in order to form a layer having a profile), a raw material gas for supplying atoms (MCNOGS) whose distribution concentration is to be changed is controlled by adjusting the gas flow rate to a desired rate of change. This is accomplished by changing the curve as appropriate and introducing it into the deposition chamber.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system is changed as appropriate by any commonly used method such as manually or by an externally driven motor.

Substances that can be used as the Si supply gas used in the present invention include S tH4, S i2 HarS is
Silicon hydride (silanes) in a gaseous state or that can be gasified, such as Hs 5i) L, Six H
a is preferred. Also, these S
i Supply raw material gas at Hz, He, Ar as necessary.
, Ne, or the like may be used after being diluted with a gas such as Ne.

Effective halogen supply gases used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, and other gaseous or gasifiable halogens. Compounds are preferred.

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

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CIF, ClF3, BrFa l
BrF5 r IFs + IFy +
Interhalogen compounds such as IC1 and IBr can be mentioned.

Specifically, the silicon compound containing a halogen atom, so-called a silane derivative substituted with a halogen atom, includes, for example, SiF4. Sit Fs, 5iC1a, 5tBr
Silicon halides such as No. 4 are preferred.

When a silicon compound containing such a halogen atom is used to form the characteristic electrophotographic light-receiving member of the present invention by a glow discharge method or an HRCVD method, silicon hydride gas is used as the Si supply gas. Even if not used, Non-8i (H,X) containing halogen atoms on the desired support
A top layer consisting of:

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

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

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the halogen atom supply gas, but in addition, halogenated gases such as HF, HCI, HBr, and Hl Hydrogen, S I H3F + S iHz Fs, 5tHF
s, 5iHz I2, 5iHzC121S iHCl
s * SI H2B r 2 , S 1HBr,
Gaseous or gasifiable substances such as halogen-substituted silicon hydrides, such as, etc., can also be mentioned as effective raw materials for forming the upper layer. Among these substances, halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming the upper layer. In the present invention, it is used as a suitable halogen supply gas.

To structurally introduce hydrogen atoms into the upper layer, in addition to the above, H2 or SiH4,5itHa can be used.

This can also be carried out by coexisting silicon hydride such as S is Hs or S 14 HIG with silicon or a silicon compound for supplying Si in a deposition chamber to generate a discharge.

To control the amount of hydrogen atoms (H) and/or halogen atoms (X) that can be contained in the upper layer, for example, the support temperature and/or the inclusion of hydrogen atoms (H) or halogen atoms (X) The amount of raw material used for this purpose introduced into the deposition apparatus system, the discharge power, etc. may be controlled.

In order to structurally introduce atoms (M) that control conductivity into the upper layer, for example, group II atoms, group V atoms, or group II atoms, group A raw material for introduction, a raw material for introducing group V atoms, or a raw material for introducing group (III) atoms is placed in a gaseous state in a deposition chamber,
It may be introduced together with other raw materials for forming the upper layer. Materials that can be used as a raw material for introducing group (III) atoms, a raw material for introducing group V atoms, or a raw material for introducing group (III) atoms may be gaseous at room temperature and pressure, or at least under layer-forming conditions. It is desirable to use a material that can be easily gasified. Specifically, as raw materials for introducing such Group Ⅰ atoms, B, H, etc. are used for introducing boron atoms.

B.H. ,B,H,,B,H,,,B,H,. , B
Boron hydride such as 6HI ff, B @ Hl 4, BF
,,BCl,.

Examples include boron halides such as BBrs. In addition, A I CIs, GaCIs, Ga (CH
m)s.

I n Cl @ , T I C1s, etc. can also be mentioned.

In the present invention, as a raw material for introducing a group V atom, P Hs is effectively used for introducing a phosphorus atom.
, hydrogen north neighbor such as P 2 H4, PH,I.

PF,,PF,,PCIn　,PCl5　,PBrs.

Examples include halogen north neighbors such as PBrs and PIm. In addition, A s Hs, A s F s + A s
C1s rAsBrs, AsF5.5bHs, 5b
Fn.

SbF,,5bC1,,5bCi,BiHs rB
iC1s r B iB r s and the like can also be mentioned as effective starting materials for introducing Group V atoms.

Hydrogen sulfide (H,
S) , SF, , SF, ,SO, ,SO,F,.

CO8, C3,, CH, SH, C, H, SH.

Mention may be made of gaseous or gasifiable substances such as C4H4S, (CH-)-S, (C-H-)*S, and the like. In addition, SeH2, SeF6 l (CHI)! Se,C
C2Hs)! Se, TeH2, TeFs 1(CH
Examples include substances in a gaseous state or which can be gasified, such as I)*Te, (c*H8)zTe, and the like.

In addition, if necessary, the raw material for introducing atoms (M) to control these conductivities is Hz I He g A r +N
It may be used after being diluted with a gas such as e.

In order to structurally introduce carbon atoms (C), nitrogen atoms (N), or oxygen atoms (0) into the upper layer, a raw material for introducing carbon atoms (C) or nitrogen atoms must be used during layer formation. The raw material for introducing (N) or the raw material for introducing oxygen atoms (0) may be introduced in a gaseous state into the deposition chamber together with other raw materials for forming the upper layer. Raw material for introducing carbon atoms (C) or nitrogen atoms (N)
As the raw material for introduction or the raw material for introducing oxygen atoms (O), those that are gaseous at normal temperature and pressure, or those that can be easily gasified under layer-forming conditions are adopted. is desirable.

Starting materials that can be effectively used as raw material gases for introducing carbon atoms (C) include saturated hydrocarbons containing C and H as constituent atoms, such as saturated hydrocarbons having 1 to 4 carbon atoms, and saturated hydrocarbons having 2 to 4 carbon atoms.
Examples include ethylene hydrocarbons, acetylene hydrocarbons having 2 to 3 carbon atoms, and the like.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C,H,), propane (CsH,), n-butane (n-C4HIQ), pentane (C6H), and ethylene hydrocarbons include ethylene (C2H4) and propylene (C,H,).

Butene-1 (C,H,), Butene-2 (C,H,).

Isobutylene (C4H, ), pentene (C6H, ).

Acetylene (C.

H2), methylacetylene (Cs H,), butyne (C
4H6), etc.

As a raw material gas containing Si, C, and H as constituent atoms, S
i (CHs) 4, S i (Ca Hs
) Examples include alkyl silicides such as a.

In addition to this, CF4. CC1,
, CH, CF, and other halogenated carbon gases.

Starting materials that can be effectively used as raw material gases for introducing nitrogen atoms (N) include nitrogen (N, ), which has N as a constituent atom, or has N and H as constituent atoms,
Ammonia (NHs), hydrazine (H2NNH
, ), hydrogen azide (HN , ).

, gaseous or gasifiable nitrogen such as ammonium azide (NH4N, ), nitrogen compounds such as nitrides and azides. In addition, nitrogen atoms (N)
In addition to the introduction of halogen atoms (X), nitrogen trifluoride (F, N), nitrogen tetrafluoride (F4
Examples include halogenated nitrogen compounds such as N, ).

Starting materials that can be effectively used as raw material gases for introducing oxygen atoms (0) include, for example, oxygen (0,), ozone (0,), and -nitrogen oxide (No).

Nitrogen dioxide (N　O, ), -nitrogen dioxide (N,O).

Nitrogen sesquioxide (N, O,), trinitrogen tetraoxide (N.

o4), nitrogen sesquioxide (N=Os), nitrogen dioxide (No
), for example, disiloxane (H) whose constituent atoms are a silicon atom (Si), an oxygen atom (0), and a hydrogen atom (H)
s SiOS iHs ) r Trisiloxane (
Examples include lower siloxanes such as Hs 5iO8iHs 08iHs ).

Germanium (Ge) or tin atoms (
In order to structurally introduce Sn), a raw material for introducing germanium (Ge) or a tin atom (
S n) The raw material for introduction may be introduced in a gaseous state into the deposition chamber together with other raw materials for forming the upper layer. As the raw material for introducing germanium (Ge) or the raw material for introducing tin atoms (Sn), those that are gaseous at normal temperature and pressure, or that can be easily gasified at least under layer-forming conditions, are used. It is desirable that

As a material that can be a source gas for supplying Ge, GeH
4, Get Hs, Gem Ha, Ge<Hlo,
Ges H,, Ges H1a+ Get H16
1Ges H,, Get H,. GeH4, GeH4, Get
Ha + Ges Ha is preferred.

In addition, GeHF5, GeHz Fz, GeHsF
, GeHCl5 , GeHz C1t , Ge1lC1
, GeHBr5 , GeHa Br= , GeHsB
r! G e H1s * G e Hx I x
+ Hydrogenated germanium halide such as G e Hs I, GeF4゜GeCl4. GeBr4. GeIa
, GeFz.

Examples include germanium halides such as GeC1z, GeBrz, and Gel1.

Substances that can be used as raw material gas for Sn supply include SnH.
4, Sna ) L, Sns Hs * 5n4Hl
o+Sns H1! l S ns Hra+ S
ny H161S ns H+*+ S n * Hx
Sn hydride in a gaseous state or that can be gasified is effectively used, such as Sn.
Ha.

Sn! Preferred examples include Ha and Snm Ha r .

In addition, 5nHFs, SnH*Fz, SnH*F
, 5nHCIs, 5nHz Clx
, SnH.

CI, 5nHBra, 5nHs Bra
, 5nHsBr, 5nH1s, 5nHx
Ia, 5nHs I, etc. hydrogenated tin halide, 5
nF4,5nC14゜SnB rA , Sn 14.5
nFs, SnC12.

Gaseous or gasifiable substances such as tin halides such as 5nBrz, SnI*, etc. may also be mentioned as useful starting materials for forming the upper layer.

The thickness of the upper layer in the present invention is 1 to 130 μm from the viewpoint of obtaining desired electrophotographic properties and economical effects.
m1 preferably 3-100 μm1 optimally 5-60 μm
It is desirable to do so.

Non-8i having characteristics that can achieve the purpose of the present invention
In order to form the upper layer consisting of (H,X), it is necessary to appropriately set the gas pressure in the deposition chamber and the temperature of the support as desired.

The optimum range of the gas pressure in the deposition chamber is appropriately selected according to the layer design, but is usually between 1X10-' and 10 Torr, preferably between IX10-' and 3 Torr.

Optimally, it is preferable to set it to lXl0-' to ITorr.

The upper layer is Non-3i (H,X) and hydrogen atoms (H
) and/or A-3 containing a halogen atom (X)
i (hereinafter abbreviated as rA-3i (H, , 50 to 400°C, preferably 100 to 300°C.

The upper layer is Non-8i (H,X) and hydrogen atoms (H
) and/or halogen atoms (X) (hereinafter abbreviated as rpoly-8i(H,X)J), there are various methods for forming the layer. There are several methods, such as the following. One method is to increase the support temperature to a high temperature.
Specifically, the temperature is set at 400 to 600° C., and a film is deposited on the support by plasma CVD.

Another method is to first form an amorphous film on the surface of a support, that is, to form a film on the support at a temperature of about 250° C. by plasma CVD, and then annealing the amorphous film. By doing po
This is a method of converting it into ly. The annealing treatment is performed by heating the support to 400 to 600° C. for about 5 to 30 minutes, or by irradiating it with laser light for about 5 to 30 minutes.

In the present invention, when the upper layer made of Non-8i (H, 5×10-6~10W/cm
3, preferably 5×10'~5W/cm'
, optimally between 1 x 10-s and 2 x 10-'W/cm
” is preferable.

In the present invention, the above-mentioned desirable numerical ranges for the gas pressure in the deposition chamber, the support temperature, and the discharge power supplied to the deposition chamber for creating the upper layer include the above-mentioned ranges, but these layer creation factors are usually are not determined independently and separately, but should be used to form an upper layer having desired characteristics (Creating an upper layer based on mutual and organic relationship [Example]) The present invention will be further illustrated by the following Examples. Although described in detail, the present invention is not limited thereto.

<Example 1> An electrophotographic light-receiving member of the present invention was formed by a radio frequency (hereinafter abbreviated as rRFJ) glow discharge decomposition method.

FIG. 37 shows a source gas supply device 1020 and a deposition device 100.
1 shows an apparatus for manufacturing an electrophotographic light-receiving member using an RF glow discharge decomposition method.

1071.1072, 1073, 1074.10 in the diagram
75,1076.1077 gas cylinder and 1078
The raw material gas for forming each layer of the present invention is sealed in the airtight container, and 1071 is a SiH4 gas (purity 99.99%) cylinder, and 1072 is a H2 gas (purity 99.99%) cylinder.
9.9999%) cylinder, 1073 is a CH4 gas (purity 99°999%) cylinder, 1074 is a PH gas diluted with H2 gas (purity 99.999%, hereinafter referred to as PH,/
(abbreviated as H, J) cylinder, 1075 is B, H, gas diluted with H, gas (purity 99°999%, hereinafter rB,
1076 is a No gas (purity 99.9%) cylinder, 1077 is a He gas (purity 99.9%).
999%) cylinder, 1078 is AlCl, (purity 99.
99%).

In the figure, 1005 is a cylindrical aluminum support, the outer diameter of which is 108 mm, and the surface of which is mirror-finished.

First, valves 1051 to 1077 of gas cylinders 1071 to 1077
1057, inflow valves 1031 to 1037, deposition chamber 10
After confirming that the leak valve 1015 of No. 01 is closed and that the outflow valves 1041 to 1047 and the auxiliary valve 1018 are open, first open the main valve 1016 and start depositing with a vacuum pump (not shown). The inside of the chamber 1001 and gas piping was evacuated.

Next, the vacuum gauge 1017 read approximately 1xlO-'T.

When rr is reached, auxiliary valve 1018 and outflow valve 1 are closed.
041-1047 closed.

After that, SiH4 gas from gas cylinder 1071, H2 gas from gas cylinder 1072, CH4 gas from gas cylinder 1073, PH and /H2 gas from gas cylinder 1074, B2H=/H2 gas from gas cylinder 1075, No gas from gas cylinder 1076, and H from gas cylinder 1077.
Introduce e-gas by opening valves 1051 to 1057,
Each gas pressure is set to 2K by pressure regulators 1061 to 1067.
g/Cm".

Next, the inflow valves 1031 to 1037 are gradually opened to supply each of the above gases to the mass flow controllers 1021 to 1021.
It was introduced within the 27th. At this time, the mass flow controller 1027 receives the He gas from the gas cylinder 1077.
AlC1 gas diluted with He gas (hereinafter rA1c
1. /HeJ) is introduced.

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

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

To form the bottom layer, the outflow valves 1041°1042
．． 1046, 1047 and the auxiliary valve 1018 are gradually opened to supply 5iHn gas, H2 gas, No gas, AlC1.
, /He gas through the gas discharge hole 100 of the gas introduction pipe 1008
9 into the deposition chamber 1001. At this time, S
iHa gas flow rate is 508CCM, H, gas flow rate is IO
8CCMSNo gas flow rate is 58CCMSAIC1,/H
e Each mass flow controller 1021.1022°1026.10 so that the gas flow rate is 1208CCM.
Adjusted at 27. The pressure inside the deposition chamber 1001 is 0.4T.
The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the temperature was 0.orr'. After that, R (not shown)
The power of the F power source is set to 5 mW/cm'' and RF power is introduced into the deposition chamber 1001 through the high frequency matching box 1012 to generate an RF glow discharge and start forming the lower layer on the cylindrical aluminum support. During the formation of the lower layer, the H gas flow rate was varied from IO8CCM to 200SCCM so that the SiH4 gas flow rate was a constant flow rate of 50SCCM.
Mass flow controllers 1021°102 are set so that the No gas flow rate increases at a constant rate to SCCM, the No gas flow rate becomes 53CCM, and the AlC1,/He gas flow rate decreases at a constant rate from 120SCCM to 40SCCM.
2.1026.1027 was adjusted and the RF glow discharge was stopped when a lower layer with a layer thickness of 0605 μm was formed, and the outflow valve 1041°1042.1046.1047
Then, the auxiliary valve 1018 was closed to stop the gas from flowing into the deposition chamber 1001, and the formation of the lower layer was completed.

Next, to form the first layer region of the upper layer, the outflow valves 1041, 1042, 1046 and the auxiliary valve 10
18 was gradually opened to allow SiH4 gas, H gas, and NO gas to flow into the deposition chamber 1001 through the gas discharge hole 1009 of the gas introduction pipe 1008. At this time, SiH, gas flow rate is 11005CC, H, gas flow rate is 11005CC
, No. gas flow rate was adjusted to 303 CCM using each mass flow controller 1021, 1022, and 1026. The pressure inside the deposition chamber 1001 is 0.35 Torr.
The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the temperature was r. Thereafter, the power of an RF power source (not shown) is set to 10 mW/cm'', and RF power is introduced into the deposition chamber 1001 through the high frequency matching box 1012 to generate an RF glow discharge, and the first layer of the upper layer is placed on the lower layer. After forming the first layer region of the upper layer with a layer thickness of 3 μm, the RF glow discharge is stopped, and the outflow valves 1041, 1042, 1046 and the auxiliary valve 1018 are closed, and the deposition chamber is closed. The flow of gas into 1001 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, 1042 and the auxiliary valve 1018 are gradually opened to supply S I Ha gas and H2 gas to the gas inlet pipe 10.
08 into the deposition chamber 1001 through the gas discharge hole 1009. At this time, the SiH4 gas flow rate was 3003CC.
Mass flow controllers 1021 and 1022 were used to adjust the M, H, and gas flow rates to 3008 CCM. While checking the vacuum gauge 1017, adjust the pressure inside the deposition chamber 1001 to 0.5 Torr by turning the main valve 1016.
Adjusted the aperture. Thereafter, the power of an RF power source (not shown) is set to 15 mW/cm", and RF power is introduced into the deposition chamber 1001 through the high frequency matching box 1012 to generate an RF glow discharge, and the first layer of the upper layer is heated. Start forming a second layer area on the area, stop the RF glow discharge after forming the second layer area of the top layer with a layer thickness of 20 μm, and close the outflow valves 1041, 1042 and the auxiliary valve 1018. Then, the flow of gas into the deposition chamber 1001 was stopped, and the formation of the third layer region of the upper layer was completed.

Next, to form the third layer region of the upper layer, the outflow valves 1041, 1043 and the auxiliary valve 1018 are gradually opened to supply S I Ha gas and CH4 gas to the gas inlet pipe 1.
008 into the deposition chamber 1001 through the gas discharge hole 1009. At this time, the SiHa gas flow rate is 50SC
Each mass flow controller 1021 and 1023 was adjusted so that the CMSCH4 gas flow rate was 5003 CCM. While checking the vacuum gauge 1017, the main valve 10 is adjusted so that the pressure inside the deposition chamber 1001 is 0.4 Torr.
16 apertures were adjusted. Thereafter, the power of an RF power source (not shown) is set to 10 mW/cm'', and RF power is introduced into the deposition chamber 1001 through the high frequency matching box 1012 to generate an RF glow discharge, thereby dissolving the second layer of the upper layer. Start forming the third layer area on the area, layer thickness 0,5μ
When the third layer region of the upper layer of m is formed, the RF glow discharge is stopped, and the outflow valves 1041, 1043 and the auxiliary valve 1018 are closed to stop the gas from flowing into the deposition chamber 1001, and the upper layer is The formation of the second layer region is completed.

Table 1 shows the conditions for producing the above electrophotographic light-receiving member.

It goes without saying that the outflow valves for gases other than those required for forming each layer are completely closed (in addition, each gas flows into the deposition chamber 1001 and outflow valve 10
In order to avoid remaining in the piping from 41 to 1047 to the deposition chamber 1001, the outflow valves 1041 to 104
7, open the auxiliary valve 1018, and then fully open the main valve to temporarily evacuate the system to a high vacuum, as necessary.

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

<Comparative Example> An electrophotographic light-receiving member was produced under the same production conditions as in Example 1, except that H2 gas and He gas were not used when forming the lower layer. Table 2 shows the conditions for producing this light-receiving member for electrophotography.

The electrophotographic light-receiving members of Example 1 and Comparative Example were set in an electrophotographic device that was a modified Canon NP-7550 copier for experimental purposes, and several tests were carried out under various conditions. When the electrophotographic properties were checked, no image defects were observed even when high voltage was applied to the electrophotographic light-receiving member due to extremely strong corona charging or frictional charging caused by cleaning agents, etc. It was found that it has remarkable characteristics regarding voltage resistance.

Next, we compared the number of spots as an image characteristic, and found that the electrophotographic light-receiving member of Example 1 was 3/4 or less of the electrophotographic light-receiving member of Comparative Example in terms of the number of spots with a diameter of 0.1 mm or less. It was found that the number of cases was as follows. Furthermore, in order to compare the degree of roughness,
Image densities were measured at 100 points with a circular area of mm mm as one unit, and the variation in image density was evaluated. The variation was 1/2 or less, and it was found that the electrophotographic light-receiving member of Example 1 was superior to the electrophotographic light-receiving member of Comparative Example even by visual inspection.

In addition, in order to compare the degree of occurrence of image defects and layer peeling of the light-receiving layer due to relatively short-term impact mechanical pressure applied to light-receiving members for electrophotography, a diameter of 3.5 m was measured.
A stainless steel ball of 30 cm was dropped freely from 30 cm vertically above the surface of the electrophotographic light-receiving member and was applied to the surface of the electrophotographic light-receiving member to measure the probability of cracks occurring in the light-receiving layer. It was found that the electrophotographic light-receiving member had a probability of occurrence of 215 or less than the electrophotographic light-receiving member of the comparative example.

As seen above, the electrophotographic light-receiving member of Example 1 was found to be comprehensively superior to the electrophotographic light-receiving member of Comparative Example.

<Example 2> The method of changing the A I Cl s / He gas flow rate was changed in the lower layer, and the BsHa gas was used in the upper layer.
An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in the table, and the same evaluation was conducted.
Similarly, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 3> In the upper layer of Example 1, CH and gas were not used, and the fourth
A light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in the table, and the same evaluation was performed. As in Example 1, it was found to be good in terms of spots, roughness, and layer peeling. The effect was obtained.

<Example 4> In Example 1, the PH, /H, and gas cylinders were replaced with He gas (
A light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 5, using SiF, gas, N, and gas from a cylinder (not shown). Similar evaluations were conducted, and as in Example 1, good effects were obtained in improving the edges, roughness, and layer peeling.

<Example 5> In Example 1, the B, H, /H, gas cylinders were changed to Ar gas cylinders (purity 99.9999%), and the No gas cylinders were changed to NH, gas (purity 99°999%) cylinders. An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 6, and the same evaluation was performed. As in Example 1, it was found to be improved in terms of edges, roughness, and layer peeling. Good effects were obtained.

<Example 6> An electrophotographic light-receiving member was prepared in the same manner as in Example 1, except that PH8/H, gas, and C-N2 gas were further used in Example 1, and according to the preparation conditions shown in Table 7. As a result of various evaluations, similar to Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 7> In the upper layer, an electrophotographic light-receiving member was produced in the same manner as in Example 1, using 51 g of gas from a cylinder not shown, and under the production conditions shown in Table 8, and the same evaluation was carried out. As a result, similar to Example 1, good effects were obtained in improving the effects of creases, roughness, and layer peeling.

<Example 8> In Example 1, N2 gas and H2S were supplied from an unillustrated cylinder.
An electrophotographic light-receiving member was prepared in the same manner as in Example 1 using a gas and under the preparation conditions shown in Table 9, and was evaluated in the same manner as in Example 1. A good effect of improving peeling was obtained.

<Example 9> In Example 1, the CH gas cylinder was replaced with a C2H2 gas (purity 99.9999%) cylinder, and a light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 10. When the film was prepared and evaluated in the same manner as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 10> In Example 1, the No gas cylinder was replaced with an N gas cylinder, and H and S gases were used from cylinders not shown in the first example.
An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 1, and the same evaluation was performed. As in Example 1, it was found to be improved against spots, roughness, and layer peeling. Good effects were obtained.

<Example 11> In Example 1, the No gas cylinder was replaced with NH, gas (purity 9
9.999%) instead of a cylinder, an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 12, and the same evaluation was performed. Good effects were obtained to improve against roughness, roughness, and layer peeling.

(Example 12) In the same manner as in Example 6, SiF4 gas was further used from a cylinder not shown in the upper layer, and the C, H, and gas cylinders were changed to CH4 gas cylinders under the production conditions shown in Table 13. A photographic light-receiving member was prepared and evaluated in the same way as in Example 6, and as in Example 6, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 13> In the upper layer, 5i2Hs gas was used from a cylinder (not shown), B, H, /H gas was further used, and electrophotographic light was produced in the same manner as in Example 9 under the production conditions shown in Table 14. A receiving member was prepared and evaluated in the same manner as in Example 9, and as in Example 9, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 14> An electrophotographic light-receiving member was produced in the same manner as in Example 11, using P Hs / H2 gas in the upper layer and according to the production conditions shown in Table 15, and the same evaluation was performed. As in Example 11, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 15> An electrophotographic light-receiving member was prepared in the same manner as in Example 1 using GeHa gas from a cylinder (not shown) in the upper layer and under the preparation conditions shown in Table 16, and the same evaluation was performed. As a result, similar to Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 16> In Example 1, the outer diameter of the cylindrical aluminum support was set to 80 mm, and an electrophotographic light-receiving member was prepared in the same manner as in Example 1 according to the preparation conditions shown in Table 17. Evaluations were conducted in the same manner as in Example 1, except that an electrophotographic device modified from a copying machine NP-9030 was used for the experiment, and as in Example 1, the problems with spots, roughness, and layer peeling were improved. Good effects were obtained.

<Example 17> In Example 1, the outer diameter of the cylindrical aluminum support was set to 60 mm, and an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 18. Evaluations were conducted in the same manner as in Example 1, except that an electrophotographic device modified from a copying machine NP-150Z was used for the experiment, and as in Example 1, the problems with spots, roughness, and layer peeling were improved. Good effects were obtained.

<Example 18> In Example 1, the outer diameter of the cylindrical aluminum support was set to 30 mm, and an electrophotographic light-receiving member was prepared in the same manner as in Example 1 according to the preparation conditions shown in Table 19. Evaluations were conducted in the same manner as in Example 1, except that an electrophotographic device modified from the FC-5 copying machine was used for the experiment.
As in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 19> In Example 1, the outer diameter of the cylindrical aluminum support was set to 15 mm, and a light-receiving member for electrophotography was prepared in the same manner as in Example 1 according to the preparation conditions shown in Table 20. Evaluations were conducted in the same manner as in Example 1, except that an electrophotographic apparatus prototyped in Example 1 was used, and as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 20> In Example 16, the mirror-finished cylindrical aluminum support was further lathe-processed using a sword bit.
With a cross-sectional shape as shown in Figure 38, a = 25 μm, b = 0.8
An electrophotographic light-receiving member was prepared using a cylindrical aluminum-based support having a diameter of μm under the same conditions as in Example 16.
Similarly, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 21> In Example 16, the mirror-finished cylindrical aluminum support was subsequently exposed to a number of drops in the bearing application, resulting in countless dents on the surface of the cylindrical aluminum support. A so-called surface dimple treatment is applied to create a surface with a cross-sectional shape as shown in Figure 39, C = 50 μm, d.
An electrophotographic light-receiving member was prepared under the same conditions as in Example 16 using a cylindrical aluminum-based support having a diameter of 1 μm, and was evaluated in the same manner as in Example 16. Good effects were obtained to improve the appearance of spots, roughness, and layer peeling.

<Example 22> In Example 9, the temperature of the cylindrical aluminum support was set to 500° C., and the upper layer was made of poly-8i (H,X) according to the preparation conditions shown in Table 21. A member was prepared in the same manner as in Example 9 and evaluated in the same manner as in Example 9. As in Example 9, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 23> An electrophotographic light-receiving member of the present invention was formed by a microwave (hereinafter abbreviated as "μW") glow discharge decomposition method.

The deposition apparatus 1000 of the production apparatus for the RF glow discharge decomposition method shown in FIG. 37 is replaced with the deposition apparatus 1100 for the μW glow discharge decomposition method shown in FIG.
An apparatus for manufacturing an electrophotographic light-receiving member by the μW glow discharge decomposition method shown in FIG.

In the figure, 1107 is a cylindrical aluminum support, the outer diameter of which is 108 mm, and the surface of which is mirror-finished.

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

Thereafter, in the same manner as in Example 1, each gas was introduced into mass flow controllers 1021 to 1027. However, PH,
/H, a SiF4 gas cylinder was used instead of a gas cylinder.

Further, the temperature of the cylindrical aluminum-based support 1107 installed in the deposition chamber 1101 was heated to 250° C. by a heating heater (not shown).

After the preparation for film formation was completed as described above, the lower layer and the upper layer were formed on the cylindrical aluminum support 1107. To form the bottom layer, the outflow valve 104
1,1042,1045°1046,1047 and the auxiliary valve 1018 are gradually opened to release SiH4 gas, H, gas, BaHs/H, gas, No gas, AlC1,/He gas into the gas introduction pipe 1110 (not shown). The plasma was allowed to flow into the plasma generation region 1109 through the hole. At this time, S
iH4 gas flow rate is 1508CCM, H gas flow rate is 20
SCCM, B, H, /H, gas flow rate is 60 ppm withstand S I H4 gas flow rate, No gas flow rate is 10300M
, each mass flow controller 1021.102 so that the AICIa/He gas flow rate is 400SCCM.
Adjusted at 2,1025°1026.1027. The opening of a main valve (not shown) was adjusted so that the pressure inside the deposition chamber 1101 was 0.6 mTorr while checking a vacuum gauge (not shown). After that, the power of the μW power supply (not shown) was increased to 0.5W.
/cm” and the waveguide section 1103 and dielectric window 1102
μW power was introduced into the plasma generation region 1109 through the plasma generating region 1109 to generate a μW glow discharge and start forming a lower layer on the cylindrical aluminum-based support 1107. During the formation of the lower layer, the H gas flow rate was varied from 20 SCCM to 500 SCCM so that the SiH4 gas flow rate was constant at 1508 CCM.
The B, H, and gas flow rates are set at a constant flow rate of 60 ppm relative to the S I Ha gas flow rate, and the No gas flow rate is set at a constant flow rate of IO8CCM so that the flow rate increases at a constant rate with respect to SCCM.AlC1, /He gas flow rate decreases at a constant rate from 400 SCCM to 80 SCCM at 0.01 μm on the support side, and 8 at 0.01 μm on the upper layer side.
Mass flow controller 1021.1022.10 to decrease at a constant rate from 0SCCM to 50SCCM
25,1026.1027 adjusted, layer thickness 0,02 μm
After forming the lower layer of
The flow of gas into the chamber was stopped, and the formation of the lower layer was completed.

Next, to form the first layer region of the upper layer, the outflow valves 1041, 1042, 1044.1045.1046
and gradually open the auxiliary valve 1018 to supply SiH4 gas,
H2 gas, SIF a gas.

B, H, gas, and No gas were flowed into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, the SiH4 gas flow rate is 3508CCM
, H2 gas flow rate is 350SCCM, and SiF4 gas flow rate is 20SCCM.

B, H, gas flow rate is 600p relative to SiH4 gas flow rate
Each mass flow controller 1021, 1022, 102 so that the pm, No gas flow rate is 133 CCM.
Adjusted to 4,1025.1026. The pressure inside the deposition chamber 1101 was adjusted to 0.5 mTorr. After that, the power of a μW power source (not shown) is set to 0.5 W/cm'', and μW is applied in the plasma generation chamber 1109 as in the lower layer.
A glow discharge was generated and the formation of the first layer region of the upper layer was started on the lower layer, forming the first layer region of the upper layer with a layer thickness of 3 μm.

Next, to form the second layer region of the upper layer, the outflow valves 1041, 1042, 1044 and the auxiliary valve 10
18 gradually open S iH4 gas, H2 gas, S i
F a gas was flowed into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110 .

At this time, the SiH4 gas flow rate is 700SCCMSH, the gas flow rate is 500SCCM, and the SiF gas flow rate is 30SCCM.
Each mass flow controller 1021
．． Adjusted with 1022.1024. The pressure inside the deposition chamber 1101 was set to 0.5 mTorr.

After that, the power of a μW power source (not shown) is set to 0.5 W/cm", and the μ
A W glow discharge was generated to start forming a second layer region of the upper layer on the first layer region of the upper layer, thereby forming a second layer region of the upper layer having a layer thickness of 20 μm.

Next, to form the third layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened to supply SiH4 gas, CH, and gas to the gas inlet pipe 11.
Plasma generation space 1 through 10 gas discharge holes (not shown)
109. At this time, the S I Ha gas flow rate was 150SCCM.

Each mass flow controller 1021 and 1023 was adjusted so that the CH and gas flow rates were 5003 CCM.

The pressure inside the deposition chamber 1101 was 0.3 mTorr.

Thereafter, the power of a μW power source (not shown) is set to 0.5 W/cm" to generate a μW glow discharge in the plasma generation region 1109, and a 1 μm thick upper layer is formed on the second layer region of the upper layer. A third layer region was formed.

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

This electrophotographic light-receiving member was evaluated in the same manner as in Example 1, and as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 24> In Example 1, CH and gas cylinders were C and H.

Change to a gas (99.9999% purity) cylinder and use the 23rd
A light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in the table, and the same evaluation was conducted. The effect was obtained.

<Example 25> An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 24 except that the No gas cylinder was replaced with a N2 gas cylinder in Example 1, and the same evaluation was performed. Similar to Example 1, good effects were obtained in improving the effects on creases, roughness, and layer peeling.

<Example 26> In Example 1, the No gas cylinder was replaced with NH, gas (purity 9
9.999%) Instead of using a cylinder, an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 25, and the same evaluation was performed. Good effects were obtained to improve against roughness, roughness, and layer peeling.

<Example 27> Example 6 was prepared according to the production conditions shown in Table 26 by further using SiF4 gas from a cylinder not shown in the upper layer.
An electrophotographic light-receiving member was prepared in the same manner as in Example 6, and the same evaluation was performed. As in Example 6, good effects were obtained in improving the edges, roughness, and layer peeling.

<Example 28> In the upper layer, the S t Ha gas cylinder is replaced with Si.

A light-receiving member for electrophotography was prepared in the same manner as in Example 9 using B, H, /H, gas instead of the H, gas cylinder, and under the preparation conditions shown in Table 27, and the same evaluation was performed. Similar to Example 9, good effects were obtained in improving the burrs, roughness, and layer peeling.

<Example 29> PH, /H2 gas is further used in the upper layer, and the second
An electrophotographic light-receiving member was produced in the same manner as in Example 11 under the production conditions shown in Table 8, and the same evaluation was performed.
Similar to Example 11, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 30> In Example 1, the PH, /H, and gas cylinders were replaced with He gas (
A light-receiving member for electrophotography was prepared in the same manner as in Example 1, using N and gas from a cylinder (not shown) and according to the preparation conditions shown in Table 29. As a result of the evaluation, as in Example 1, good effects were obtained in improving the effects of creases, roughness, and layer peeling.

<Example 31> In the upper layer, C2H2 gas, S
An electrophotographic light-receiving member was produced in the same manner as in Example 1 using iF4 gas and under the production conditions shown in Table 30, and the same evaluation was performed.
A good effect of improving roughness and layer peeling was obtained.

<Example 32> Example 31 was prepared by further using 5iFa gas from a cylinder not shown in the upper layer and under the production conditions shown in Table 31.
An electrophotographic light-receiving member was prepared in the same manner as in Example 31, and the same evaluation was performed. As in Example 31, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 33> Using B2H, /H2 gas, C,
A light-receiving member for electrophotography was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 32 using H, gas, and the same evaluation was performed.
A good effect of improving roughness and layer peeling was obtained.

<Example 34> Using PH3/H gas, C, H,
An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 33 using additional gas, and the same evaluation was performed. A good effect of improving roughness and layer peeling was obtained.

<Example 35> A light-receiving member for electrophotography was prepared in the same manner as in Example 1 by further using C2H2 gas, SiFa gas, H, and S gas from a cylinder not shown, and under the production conditions shown in Table 34. was prepared and subjected to similar evaluations, and as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 36> Example 9 was prepared by further using C, H2 gas, and SiF4 gas from a cylinder not shown, and under the production conditions shown in Table 35.
An electrophotographic light-receiving member was prepared in the same manner as in Example 9, and the same evaluation was performed. As in Example 9, good effects were obtained in improving the edges, roughness, and layer peeling.

<Example 37> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 36, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 38> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 37, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 39> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 38, and the same evaluation was performed. A good effect was obtained that improved the results.

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

<Example 41> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 40, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 42> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 41, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 43> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 42, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 44> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 43, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 45> PH and gas were further used from a cylinder not shown, and the 44th
A light-receiving member for electrophotography was produced in the same manner as in Example 36 under the production conditions shown in the table, and the same evaluation was performed. As in Example 36, it was found to be good in terms of spots, roughness, and layer peeling. The effect was obtained.

<Example 46> An electrophotographic light-receiving member was produced in the same manner as in Example 45 under the production conditions shown in Table 45, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 47> H and S gases were further used from a cylinder not shown, and the 46th
A light-receiving member for electrophotography was produced in the same manner as in Example 36 under the production conditions shown in the table, and the same evaluation was performed. As in Example 36, it was found to be good in terms of spots, roughness, and layer peeling. The effect was obtained.

<Example 48> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 47, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 49> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 48, and evaluated in the same manner as in Example 36. Good effect improved against <Example 50> NH and gas are further used from a cylinder not shown, and the 49th
An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in the table, and the same evaluation was performed. As in Example 36, it was found to be good in terms of edges, roughness, and layer peeling. The effect was obtained.

<Example 51> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 using N2 gas from a cylinder (not shown) and under the preparation conditions shown in Table 50, and the same evaluation was performed. Similar to Example 36, good effects were obtained to improve the effects on creases, roughness, and layer peeling.

<Example 52> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 51, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 53> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 52, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 54> An electrophotographic light-receiving member was produced in the same manner as in Example 45 under the production conditions shown in Table 53, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 55> An electrophotographic light-receiving member was produced in the same manner as in Example 36 under the production conditions shown in Table 54, and the same evaluation was performed. A good effect was obtained that improved the results.

Table 1 Table 2 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8 Table 9 Table 10 Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 17 Table 18 Table 19 Table 20 Table 21 Table 22 Table 23 Table 24 Table 25 Table 26 Table 27 Table 28 Table 29 Table 30 Table 31 Table 32 Table 33 Table 34 Table 35 Table 36 Table 37 Table 38 Table 39 Table 40 Table 41 Table 42 Table 43 Table 44 Table 45 Table 46 Male Table 47 Table 48 Table 49 Table 50 No. 52 Harm [Effect of the Invention] By making the electrophotographic light receiving member of the present invention have the specific layer structure as described above, all the problems in the conventional electrophotographic light receiving member made of A-8t can be solved. In particular, extremely excellent electrical properties, optical properties,
Indicates photoconductive properties, image properties, durability and use environment properties.

In particular, in the present invention, the lower layer contains aluminum atoms (AI), silicon atoms (Si), and especially hydrogen atoms (H) in a non-uniform distribution state in the layer thickness direction, and atoms ( By incorporating CNOc),
In order to improve the injection property of charge (photo carrier) between the aluminum-based support and the upper layer, and further improve the structural continuity of the constituent elements of the aluminum-based support and the upper layer. , image characteristics such as roughness and blur are improved, halftones appear clearly, and high-quality images with high resolution can be stably and repeatedly obtained.

Furthermore, image defects and non-contamination may occur due to relatively short-term impact mechanical pressure applied to electrophotographic light-receiving members.
It prevents the occurrence of peeling of the 5i (H,
Alleviates stress caused by the difference in thermal expansion coefficient of n-5i (H,X) film, prevents cracks and peeling of Non-Si (H, be able to.

Furthermore, in the present invention, the adhesion between the upper layer and the lower layer is further improved by containing at least one atom among carbon atoms, nitrogen atoms, and oxygen atoms in the layer region in contact with the lower layer in the upper layer. The occurrence of image defects and Non-3i (H.

X) Prevents peeling of the film and further improves durability.

[Brief explanation of the drawing]

FIG. 1 is a schematic block diagram for explaining the layer structure of a light-receiving member for electrophotography according to the present invention. FIG. 2 is a schematic block diagram for explaining the layer structure of a conventional light-receiving member for electrophotography. , Figures 3 to 8 respectively show aluminum atoms (AI) contained in the lower layer and durability adjusting atoms (CNO).
c), atoms (M
Figures 9 to 16 are explanatory diagrams of the distribution state of c), respectively, silicon atoms (Si), hydrogen atoms (H), and durability adjusting atoms (CNOc) contained in the lower layer, if necessary. Figures 17 to 36 are explanatory diagrams of the distribution state of atoms (M c ) that adjust the image quality, respectively. /
or nitrogen atom (N) and/or oxygen atom (O),
Germanium atoms (Ge) and/or tin atoms (S
Fig. 37 is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method using RF, which is an example of an apparatus for forming the light-receiving layer of the electrophotographic light-receiving member of the present invention. , FIG. 38 is an enlarged view of the cross section of the aluminum support when the cross-sectional shape of the aluminum support is V-shaped when forming the electrophotographic light receiving member of the present invention, and FIG. 39 is an enlarged view of the cross section of the support for forming the electrophotographic light receiving member of the present invention FIG. 40 is an enlarged view of a cross section of the support when the surface of the aluminum support is subjected to a so-called dimple treatment when forming a light-receiving member. FIG. FIG. 41 is a schematic explanatory diagram of a deposition apparatus using a microwave glow discharge method for forming a light-receiving layer of a light-receiving member for electrophotography according to the present invention. FIG. 2 is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method. Regarding FIG. 1, 100...Light receiving member for electrophotography of the present invention 101...
・Aluminum support 102...Light-receiving layer 103...Lower layer 104...Upper layer 105...Regarding the free surface in FIG. 2, 200...Conventional light-receiving member for electrophotography 201...・
Aluminum support 202...Photosensitive layer 203 made of A-Si...Free surface In FIG. 37, 1000...Deposition device 1001 by RF glow discharge decomposition method...Deposition chamber 1005...Cylindrical shape Aluminum support 1008・
...Gas inlet 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...Material gas supply device 1021-1027...Mass flow controller 1031-1037...Gas Inflow valve 1041-1
047...Gas outflow valve 1051-1057...
Valve 1061 to 1067 of raw material gas cylinder... Pressure regulator 1071 to 1077... Raw material gas cylinder 1078...
・Hermetically sealed container for raw materials In FIGS. 40 and 41, 1100...deposition device 1101 using microwave glow discharge method...deposition chamber 1102...dielectric window 1103...waveguide section 1107... Cylindrical aluminum support 1109
...Plasma generation area 1010...Gas introduction pipe

Claims (2)

[Claims] (1) In a photoreceptive member having an aluminum-based support and a photoreceptive layer having a multilayer structure exhibiting photoconductivity on the support, the photoreception layer has at least aluminum atoms and silicon atoms as constituent elements from the support side. atom, hydrogen atom,
a lower layer made of an inorganic material containing atoms that adjust durability and having a portion containing the aluminum atoms, silicon atoms, and hydrogen atoms in a non-uniform distribution in the layer thickness direction; It is composed of a non-single crystal material containing at least one of atoms and halogen atoms, and contains at least one kind of atoms among carbon atoms, nitrogen atoms, and oxygen atoms in the layer region in contact with the lower layer. A light-receiving member comprising an upper layer. (2) The light-receiving member according to claim 1, wherein the atom that adjusts durability is at least one of a carbon atom, a nitrogen atom, and an oxygen atom.