JPS63274963A - 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 on an Al supporting body. CONSTITUTION:The photoreceptive layer 102 consisting of the lower layer 103 of the inorg. material (AlSiH) contg. the Al atom, Si atom, and H atom unevenly distributed in the thickness direction and the CNOc atom for regulating durability and the upper layer 104 of the non-crystal material [non-Si(H,X)] with an Si atom as the matrix and contg. at least one between an H atom and a halogen (X) atom is formed on the Al supporting body 101. By this layer formation, the charge injectability between the supporting body 101 and the layer 104 and the structural continuity of the component elements with the supporting body 101 and the layer 104 are improved, a high-resolution picture image having a clear halftone is obtained, the durability is improved, the stress due to the difference in the thermal expansion coefficients of the supporting body 101 and layer is relieved, and the productivity is enhanced.

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 must have 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-5i) is a photoconductive material that has recently attracted attention.
Application as a light-receiving member for electrophotography is described in JP 855718 and the like.

FIG. 2 is a cross-sectional view schematically showing the layer structure of a conventional electrophotographic light-receiving member, in which 201 is an aluminum support and 202 is a photosensitive layer made of A-8i. 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 differ by about one order of magnitude, cracks and peeling may occur in the A-8i sensitive light 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-based support, an intermediate layer containing a small amount of aluminum, and an A-3i photoreceptor. The aluminum-based support and the A-8i
It relieves the stress caused by the difference in thermal expansion coefficients of the A-8i sensitive skin, and reduces cracks and peeling of the A-8i sensitive skin.

[Problem that the invention seeks to solve]

However, electrophotographic light-receiving members having a light-receiving layer composed of conventional A-8i 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 "bodies" 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 in that the durability of the electrophotographic light-receiving member is impaired due to the occurrence of image defects and the occurrence of peeling of the A-3t 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-3i film, resulting in a reduction in productivity and yield.

Therefore, while efforts are being made to improve the properties of the A-8t material itself, when designing an electrophotographic light receiving member, it is important to consider the overall structure of the electrophotographic light receiving member so that all of the above-mentioned problems are solved. 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 has an aluminum support and a multilayer light-receiving layer having at least photoconductivity on the support. In the light-receiving member, the light-receiving layer includes, from the support side, an inorganic material containing at least aluminum atoms (A1), silicon atoms (Si), hydrogen atoms (H), and durability-adjusting atoms (CNOc) as constituent elements. (hereinafter abbreviated as "Al5iH") and has a portion containing the aluminum (A1), silicon atoms (Si), and hydrogen atoms (H) in a non-uniform distribution state in the layer thickness direction. , a non-single-crystalline material (hereinafter abbreviated as rNon-8i (H, ) is characterized by an upper layer consisting of

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. 1 Image characteristics, durability, and use environment characteristics are shown.

Especially in the lower layer 1. By containing aluminum atoms, silicon atoms, and especially hydrogen atoms in a non-uniform distribution in the layer thickness direction, and by containing atoms (CNO,') that adjust durability, the bond between the aluminum support and the upper layer is improved. The injection properties of charge (photocarriers) between the aluminum support and the upper layer are improved, and the structural continuity of the constituent elements between the aluminum support and the upper layer is improved, so image characteristics such as roughness and spots are reduced. It is possible to stably and repeatedly obtain high-quality images with improved halftones and high resolution.

Furthermore, a remarkable feature of the durability-adjusting atom content is that it significantly improves the durability against relatively short-term impact mechanical pressure that is applied to electrophotographic light-receiving members. It prevents the occurrence of peeling of the 8i (H, Relax, Non-3i (
It is possible to prevent the occurrence of cracks and peeling in the H,

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, The present invention and [Detailed Description of the Invention] Hereinafter, the electrophotographic light receiving member of the present invention will be described in detail by giving specific examples 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;
5i(H,X), and a photoreceptive layer 102 having a layered structure. Upper layer 104
has a free surface 105.

Aluminum-based 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 type, composition, etc. of the □ component can be arbitrarily selected. Therefore, the aluminum alloy of the present invention has Japanese Industrial Standards (
JIS), AA standards, BS standards, DIN standards, international alloy registration, etc., which are standardized or registered as wrought materials, castings, die castings, etc., pure aluminum, ^1-Cu, Al-In, Al-5t series, At-Mg series, Al-
Alloys with compositions such as Mg-5i series, ^1-Zn -Mg series, Al-Cu-Mg series (duralumin, super duralumin, etc.), Al-Cu-3i 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
O, 10% by weight or less, AI 99.00% by weight or more.

As the Al-Cu-Mg system, for example, JIS 2017, SiO, 05 to 0.20% by weight, FeO, 7% by weight or less, Cu 3.5 to 4.5% by weight, )in 0.40 to
1.0% by weight, MgO, 46-0.8% by weight, Zn
Examples include O, 25% by weight or less, Cr O, 10% by weight or less, and the balance A1.

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 AI 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 18-1.3% by weight, Zn 0.25% by weight or less, CrO, 10
% by weight or less, NiO, 5 to 1.3% by weight, balance Al.

As the Al-Mg system, for example, JIS508.6, S
i0.40% by weight or less, FeO, 50% by weight or less,
Cu O, 10% by weight or less, Mn O, 2 (1 to 0
．． 7% by weight, Mg 3.5-4.5% by weight, ZnO
, 25% by weight or less, CrO, 05-0.25% by weight
, TiO, 15% by weight or less, and the remainder A1.

Furthermore, Si 0.50% by weight or less, FeO,
25% by weight or less, CuO, 04-0.20% by weight,
Mn 0.01-1.0% by weight, MgO, 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, ) I, 1.0 cc or less per 100 grams of Al, the balance being A1.

Further, Si 0.12% by weight or less, Fed
, 15% by weight or less, Mn 0.30% by weight or less, M
g O, 5-5.5% by weight, Zn 0.01-1.0
Weight % or less, Cr 0.20 weight % or less, Zr O
, 01 to 0.25% by weight or less, and the remainder A1.

As the Al-Mg-3i 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
Examples include O, 10% by weight or less, and the remainder A1.

As the Al-Zn-Mg system, for example, Seal 57NO1,
Si 0.30% by weight or less, Fe O, 35% by weight or less, Cu O, 20% by weight or less, Mn 0.20-0
．． 7% by weight, Mg 1.0-2.0% by weight, Zn 4.0
~5.0% by weight, Cr 0.30% by weight or less, Ti
0.20% by weight or less, Zr 0.25% by weight or less,
Vo, 10% by weight or less, balance 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 layer The lower layer in the present invention is composed of an inorganic material containing at least aluminum atoms (AI), silicon atoms (Si), hydrogen atoms (H) and durability adjusting atoms (CNOc) as constituent elements, and Adjust the image quality according to atoms (
Mc) may be contained.

Aluminum atoms (Al), 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 (Mc
) may be contained in the entire area of the lower layer in a uniformly distributed state, or evenly distributed in the entire area of the lower layer (although it is contained, it may be unevenly distributed in the layer thickness direction). There may be a portion containing it in a uniformly distributed state.However,
In either case, it is necessary to have a uniform distribution and no bias in the in-plane direction parallel to the surface of the support in order to make the properties uniform in the in-plane direction.

Further, in one of the preferred embodiments, aluminum atoms (A1) and silicon atoms (S
i), the distribution state of hydrogen atoms (H) is such that aluminum atoms (A1), silicon atoms (Si), and hydrogen atoms (H) are continuously and evenly distributed in the entire layer region, and aluminum atoms (A1) The distribution concentration in the layer thickness direction decreases from the support side toward the upper layer, and silicon atoms (S
i) Since the distribution concentration of hydrogen atoms (H) in the layer thickness direction increases from the support side toward the upper layer, the compatibility between the aluminum support and the lower layer and between the lower layer and the upper layer is improved. Excellent in sex.

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 (Si) 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 (AI) contained in the lower layer of the electrophotographic light receiving member of the present invention.
), a typical example of the distribution state of the durability adjusting atom (CNOc), and the image quality adjusting atom (MC) contained as necessary in the layer thickness direction.

In Figures 3 to 8, the horizontal axis is the aluminum atom (
AI) (hereinafter abbreviated as [atomic (Al) J), durability adjusting atom (CNOc) (hereinafter abbreviated as [atomic (Al)
abbreviated as "c)~"), atoms (Me) that adjust image quality (
Hereinafter, it will be abbreviated as “atom (Mc)”, and atom (AI) and atom (C
NOc) and atoms (Mc') are collectively called ``atomic (AC)J
It is abbreviated as However, the distribution state of atoms (AI), atoms (CNOc), and atoms (Mc) in the layer thickness direction may be the same or different), and the vertical axis represents the layer thickness of the lower layer. tn is the position of the end surface of the lower layer on the support side, t
T 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 tIl side toward the t layer 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 ts+, which is the concentration C31.
A distribution state is formed such that the concentration C11 decreases in a linear function from the position tll to the position t7, and reaches the concentration CI2 at the position t7.

In the example shown in FIG. 4, the distribution concentration C of the contained atoms (AC) is the concentration C from position tll to position ta.
The concentration decreases linearly from 41 to C4m at position t7.

In the example shown in FIG. 5, the distribution concentration C of the contained atoms (AC) is the concentration C0 from position t to position t7.
The concentration C gradually and continuously decreases from t to t7.
1, forming a distribution state.

In the example shown in FIG. 6, the distribution concentration C of the contained atoms (AC) is from position t to position ts+, which is the concentration C61.
A distribution state is formed in which the density decreases from the density C6 to the density Csa from the position js+ to the position ta, and reaches the density Csa at the position t7.

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 ty+, and from position ty+ to position ta, the concentration C7, The concentration gradually and continuously decreases from 1 to 2, forming a distribution state in which the concentration Cys is reached at position ta.

In the example shown in FIG. 8, the distribution concentration C of the contained atoms (AC) is the concentration CI+ from position t to position 1T.
The concentration C gradually and continuously decreases from t to t7.
A distribution state is formed in which the number is 1.

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 appropriately 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 (MeCNoc), and optionally contained atoms (MC) are shown as typical examples of the distribution state 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, the distribution state of silicon atoms (Si), hydrogen atoms (H), atoms (CNOc), and atoms (MC) in the layer thickness direction is the same. The vertical axis indicates the layer thickness of the lower layer, t indicates the position of the end surface of the lower layer on the support side, and t7 indicates the position of the lower layer on the upper layer side. In other words, the lower layer containing atoms (SHC) is formed from the t side toward the 1T 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 for one hour from the concentration C91 from the position t11 to the positions t and l, and from the position t91 to the position t a. Until then, a distribution state is formed that takes a constant value of concentration C, .

In the example shown in FIG. 10, the atoms contained (SHC)
The distribution concentration C of is the concentration C0 from position t to position tT.
A distribution state is formed in which the concentration increases linearly from 1° to a concentration of C3° at position 11.

In the example shown in FIG. 11, the atoms contained (SHC)
The distribution density C gradually and continuously increases from the density C+++ from the position 1++ to the position tv, and forms a distribution state in which the density C+++ is reached at the position 11.

In the example shown in FIG. 12, the atoms contained (SHC)
The distribution concentration C increases numerically from the concentration C1,1 for one hour from the position tll to the position t121, becomes the concentration C2,2 at the position t1,1, and increases from the position t2゜1 to the position t7.
Until then, a distribution state is formed that takes a constant value of concentration C13.

In the example shown in FIG. 13, the contained atoms (SHC)
The distribution density C gradually and continuously increases from the density C11 until reaching the position t, t13, becomes the density C1,2 at the position t1,1, and reaches the density C1,2 at the position t18. A distribution state is formed in which the concentration takes a constant value of Cls* up to position ta.

In the example shown in FIG. 14, the contained atoms (SHC)
The distributed concentration C gradually and continuously increases from the concentration CI41 to the position t and then to the position tT, and forms a distribution state in which the concentration C14 is reached at the position t7.

In the example shown in FIG. 15, the contained atoms (SHC)
The distribution concentration C of is substantially zero from position t to position tlfi+ (here, substantially zero 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 CIll gradually increases from t3,1 to
From position t15+ to position t7, the concentration C,
, , forms a distribution state that takes a certain value.

In the example shown in FIG. 16, the contained atoms (SHC)
The distribution concentration C gradually increases from substantially zero from position ts to position t7, and reaches the concentration C36 at position t7.
, 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 low distribution concentration C of silicon atoms (Si) and hydrogen atoms (H), and at the interface 11, the silicon atoms (Si) have a portion where the distribution concentration C is considerably higher than that on the support side. A preferred example is formed in the case where a distribution state of hydrogen atoms (Si) and hydrogen atoms (H) is provided in the lower layer. In this case, the maximum value Cmax of the distribution concentration of the sum of silicon atoms (Si) and hydrogen atoms (H) is preferably 10 atomic % or more, more preferably 30 atomic % or more, and optimally 50 atomic % or more. It is desirable that the layers be formed so that they can be distributed in such a manner.

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 %.

The atom (CNO,') that adjusts the durability is as follows:
A carbon atom (C), a nitrogen atom (N), and an oxygen atom (0) are used. In the present invention, carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) are contained in the lower layer as atoms (CNoc) for adjusting durability, so that the aluminum-based support is mainly It is possible to obtain the effect of improving the charge injection property between the aluminum support and the upper layer, the effect of improving the running property in the lower layer, and/or the effect of improving the adhesion between the aluminum support and the upper layer. can. 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 the durability adjusting atoms (CNOc) contained in the lower layer is preferably 1X10I to 5X10' atomic ppm, more preferably 5x1O' to 4x1O' atomic ppm.

Optimally, it is desirable that the content be between 1X10'' and 3X10'' atoms ppm.

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

There are TI (thallium) 2, etc., especially B and AI.

Ga is preferred. Specifically, the Group V atoms include:
P (phosphorus), As (arsenic), Sb (antimony), Bi (
bismuth), and P and As are particularly preferred. Chapter V
Specific examples of group I atoms include S (sulfur), Se (selenium), Te (tellurium), and Po (boronium), and in particular S.

Se is preferred. In the present invention, by containing a group Ⅰ atom, a group V atom, or a group vI atom as an atom (Mc) for adjusting image quality in the lower layer, the electric charge is mainly caused between the aluminum support and the upper layer. It is possible to obtain the effect of improving the injection property and/or the effect of improving the charge mobility in the lower layer. Furthermore, the effect of controlling the conductivity type and/or conductivity can be obtained in a layer region in which the content of aluminum atoms (A1) is low in the lower layer. The content of atoms (M,) that adjusts the image quality contained in the lower layer is preferably l
Xl0-'' to 5X10' atomic ppm, more preferably l
Xl0-' ~ lXl0' atoms ppmN Optimally lXl
Preferably, it is between 0-' and 5X10'' atomic ppm.

In the present invention, the lower layer composed of AlSi■ 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. be done. 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, vacuum evaporation method, ion blating method, optical CVD method,
It can be formed by a number of thin film deposition methods such as. 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 be used in combination within the same device system. For example, by glow discharge method, Al5
In order to form the lower layer composed of iH, basically a raw material gas for supplying A1 that can supply aluminum atoms (A1), a gas for supplying Si that can supply silicon atoms (Si), and hydrogen an H supplying gas capable of supplying atoms (H);
CNO, which can supply atoms that improve durability (CNOc);
, adjust the supply gas and image quality as necessary (MC”
) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber. A layer made of Al5iH may be formed on the surface of the support.

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 CNO supply gas that can supply atoms (CNO, ) for adjusting durability;
M can supply atoms (Mc) to adjust the image quality as needed. Supply gas is introduced into the 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 (AI) and silicon atoms (Si) contained in the layer are
, hydrogen atom (H) durability adjusting atom (CNOC)
, an atom (Mc) 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 (ASH
) to form a layer having a desired depth profile in the layer thickness direction, first, as in the case of the glow discharge method, atomic (A S H) This is accomplished by using the raw material for supply 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.

Substances that can be used as the source gas for A1 supply used in the present invention include AlCl5, AlBr5゜Al1
．． , AI (CHI), CI, AI (CH,)! .

Al (OCH,),,AI (C,H8)S,AI(
QC2Hs ) s , AI (i -Cm He
) * , AI(i-Cs Ht ) , r AI (
Cs Hz ) s + AI (QC, H, ), etc. can be cited as effective examples. In addition, these raw material gases for AI supply can be converted to H2, He, Ar, etc. as necessary.
, Ne, or the like may be used after being diluted with a gas such as Ne.

Substances that can be used as the raw material gas for supplying Si used in the present invention include silicon hydride (silanes) in a gaseous state or which can be gasified, such as S i H4, S i 2 H6 °S 1sHs, 5i4H + o, etc. It is cited as being used effectively, and is also easy to handle during layer creation work,
SiH4,5izHs is preferred from the viewpoint of good Si supply efficiency. In addition, these raw material gases for Si supply may be adjusted to Hz, He, Ar, Ne, etc. as necessary.
It may be used after being diluted with gas such as.

Substances that can be used as raw material gas for hydrogen supply used in the present invention include H3, 5tH4, 5t2H
a, 5isHs, 5i4H+.

Silicon hydrides (silanes) such as the following are 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 that adjust durability (CNOC) such as carbon atoms (C), nitrogen atoms (N)', or oxygen atoms (0) into the lower layer, carbon atoms (CNOC) must be added during layer formation. C) A raw material for introduction, a raw material for nitrogen atom (N) introduction, or a raw material for oxygen atom (0) introduction in a gaseous state in a deposition chamber together with other raw materials for forming the lower layer. Just introduce it. carbon atom (C)
Materials that can be used as a raw material for introduction, a raw material for nitrogen atom (N) introduction, or a raw material for oxygen atom (0) introduction include those that are in a gaseous state at normal pressure or that are at least under layer-forming conditions. It is desirable to use a material that can be easily gasified.

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 (C.

H, ), n-butane (n Ca Hto) *Pentane (C5H10), ethylene hydrocarbons include ethylene (C, H,'), propylene (Cs H,).

Butene-1 (C4H,), Butene-2 (C4H,).

Isobutylene (C,H,), pentene (C@H,,).

Acetylene (C.

H7), methylacetylene (C,H,), butyne (C4
H, ), etc.

As a raw material gas containing Si, C, and H as constituent atoms, S
i (CHs) a + S i (C2Ha)
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, CF, and other halogenated carbon gases.

Raw 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 (NH,), Hydrazine (H, NNH,
), 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 (Fs N), nitrogen tetrafluoride (F,
Examples include halogenated nitrogen compounds such as N, ).

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

Nitrogen dioxide (N O2), -nitrogen dioxide (Nff O)
.

Nitrogen sesquioxide (N, O,), trinitrogen tetraoxide (N 504
), nitrogen sesquioxide (N, os ), nitrogen dioxide (No,
), for example, disiloxane (H8
S 10 S iHs ) + ) disiloxane (H
Examples include lower siloxanes such as s S i O8i Hz O8i Hs ).

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, 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 during layer formation. 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
Materials that can be used as raw materials for introducing group atoms or for introducing group V atoms should be those that are gaseous at room temperature and pressure, or that can be easily gasified under layer-forming conditions. It is desirable that

Specifically, BiHa is used as a raw material for introducing boron atoms as a raw material for introducing Group Ⅰ atoms.

B.H. ,B,H,,Be H,,,B,H,,,B
.

Boron hydride, BF such as Hl 2 + B 8 Hl 4
, , BCl, , BBrs, and other boron halides. In addition, AlC1,, GaC1,, Ga (CH
N)$, InC1g, 'r1cis, 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 ratio next to P, H, etc., PH.

1. PFs, pF, , Pc1s, PCl5. PBrs
, P B rs , P I j and the like are listed. In addition, AsHs, AsF5, AsCl
5, AsBr, , AsFa, 5bHs, 5bFs
, 5bFs , 5bC1, , 5bC1s , BiHs
, B1C1*, B1Br1, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

Hydrogen sulfide (H
2S), SF4. SF, , So, , So
.

F,,CO3,C82,CH,5HC2Hs SH,C
,H,S,(CH,),S(C,H,).

Substances that are in a gaseous state or can be gasified, such as S, may be mentioned. Besides this, S e H! l S e −F s +
(CHs)! Set (Ct Hs)
* S et TeHz l TeFa + (CH
Examples include substances in a gaseous state or which can be gasified, such as s )*Te, (Ct Hs ) 2 Te, and the like.

Further, the raw material for introducing atoms (Mc) for controlling the image quality may be diluted with a gas such as H2, He, Ar, Ne, etc. as necessary.

The layer thickness of the lower layer in the present invention is O, OO3, 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 (AI) 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 is because in a composition range where the content of aluminum atoms (A1) is 5% or less, its function is almost only that of an upper layer.

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

The optimum range of gas pressure in the deposition chamber is selected according to the layer design, but usually it is 1 x 10-11 to 10 Torr.
r, preferably 1 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/crrf. , preferably 5 X 10-'~5W/crd, optimally 1
It is desirable to set it to xlO-'~2xlO-'W/cm'.

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 are not determined independently and separately (to form a lower layer with desired properties).Based on the mutual and organic relationship, the upper layer in the present invention is a non-contact layer. -3i(H.

X) and has desired photoconductive properties.

In the present invention, atoms (M) controlling conductivity, carbon atoms (C
), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge), and tin atoms (S n) are substantially not contained. However, in other layer regions of the upper layer, atoms (M) that control conductivity, carbon atoms (C)
, nitrogen atom (N), oxygen atom (0), germanium atom (Ge), and tin atom (S n). In particular, the layer region near the free surface of the upper layer preferably contains at least one of carbon atoms (C), nitrogen atoms (N), and oxygen atoms (0).

At least one type of atom (M), carbon atom (C), nitrogen atom (N), oxygen atom (0), germanium atom (Ge), or tin atom (S n) that controls conductivity in the layer region of the upper layer. When containing, the atom (M) that controls the conductivity, carbon atom (C), nitrogen atom (N), oxygen atom (
0), germanium atoms (Ge), and tin atoms (Sn) may be distributed uniformly in the layer region, or they may be contained evenly in the layer region; There may be a portion where the content is distributed non-uniformly in the thickness direction.

However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary to have a uniform distribution and no bias (it is also necessary to make the properties 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 a layer region (hereinafter referred to as "layer region") containing carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) (hereinafter abbreviated as "atoms (CNO) (abbreviated as (CNO)J), germanium atom (abbreviated as
Ge) and/or tin atoms (Sn) (hereinafter referred to as [atoms (
The layer regions (hereinafter abbreviated as "layer regions (GS) J") containing the "layer regions (GS) They may be shared, or the respective layer regions may not be substantially shared.

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.

(Hereafter, layer region (M), layer region (CNO), layer region (
GS) is represented by “layer region (Y)”, and atoms (M)
, Atom (CNO), Atom (GS)
Y)”. Therefore, 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. (M), layer region (CNO), and layer region (GS) are substantially the same layer region, the layer region (Y) is included singularly in the upper layer, and is substantially the same layer region. If there is no layer region (Y), 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. The position of -, t7 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 from the t side to t7
layered towards the sides.

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 C8 from position tn to position ta.
7, a distribution state is formed in which the concentration increases gradually and continuously to reach the concentration Cm at the position t7.

In the example shown in FIG. 18, the distribution concentration C of the contained atoms (Y) increases numerically for one hour from the concentration C18 from position tB to position tIII, and increases numerically from position t31 to position tIII. A distribution state is formed in which the density becomes C+si at the position tII+ and the density takes a constant value C783 from the position tII+ to the position t7.

In the example shown in FIG. 19, the distribution concentration C of the contained atoms (Y) has a constant value of concentration C from position t8 to position t1,1, and from position t191 to position t00. A distribution state is formed in which the concentration increases gradually and continuously from CIll until reaching , and reaches the concentration C8,2 at position t5.2, and takes a constant value of concentration C,93 from position t1.2 to position t7. are doing.

In the example shown in FIG. 20, the distribution concentration C of the contained atoms (Y) is from position t to position t. The density becomes a constant value of C2°1 until it reaches the position t. , from position t
,. The density becomes a constant value of C2°2 until reaching the position t. From 2 to position ty, a distribution state is formed in which the concentration takes a constant value of C7°3.

In the example shown in FIG. 21, the distribution concentration C of the contained atoms (Y) is the concentration C2+ from position tIl to position 11.
A distribution state is formed that has a constant value of 1.

In the example shown in FIG. 22, the distribution concentration C of the contained atoms (Y) is the concentration C2 from the position ta to the position t22°.
3, and gradually and continuously decreases from the concentration C222 from the position t221 to the position ta, forming a distribution state in which the concentration reaches the concentration C22 at the position tT.

In the example shown in FIG. 23, the distribution concentration C of the contained atoms (Y) is the concentration C2 from position t to position 11.
A distribution state is formed in which the concentration gradually and continuously decreases from 11 to a concentration C2 at position t7.

In the example shown in FIG. 24, the distribution concentration C of the contained atoms (Y) is C! from position ta to position t241.
4. From position t241 to position ta, the concentration C24 gradually and continuously decreases, and at position t7, the distribution concentration C becomes substantially zero (substantially zero here means the detection limit). (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 from the position t to the concentration C2 up to the position ta.
, , , the distribution concentration C gradually and continuously decreases, forming a distribution state in which the distribution concentration C becomes substantially zero at the position ta.

In the example shown in FIG. 26, the distribution concentration C of the contained atoms (Y) is from position t to position t3,1, where the concentration C1 is
The concentration C361 decreases in a linear function from 61 to position t7, and the concentration C361 decreases linearly to position t.
7, a distribution state is formed such that the concentration is C36.

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

In the example shown in FIG. 28, the distribution concentration C of the contained atoms (Y) is from position t to position t211.
Take a constant value of 2g1 and move from position t281 to position tT.
A distribution state is formed in which the concentration decreases in a linear function from the concentration C781 until reaching the concentration C282 at the position tT.

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.
, 1 gradually and continuously decreases, forming a distribution state in which the concentration reaches C3° at position t7.

In the example shown in FIG. 30, the distribution concentration C of the contained atoms (Y) is from position t to position t. .

Until then, the concentration takes a constant value of C8°, and the position tsol
From there, up to position 11, the concentration decreases linearly from Csow, and at position t7, the concentration C. A distribution state of 3 is formed.

In the example shown in FIG. 31, the distribution concentration C of the contained atoms (Y) increases gradually and continuously from the concentration CIll from the position t to the position ts++, and becomes the concentration C□ at the position ti11. , from position t3□ to position tT, a distribution state is formed that takes a constant value of concentration C31.

In the example shown in FIG. 32, the distribution concentration C of the contained atoms (Y) is the concentration C3 from position t to position t7.
A distribution state is formed in which the concentration gradually and continuously increases from 2, to reach the concentration C, 22 at position t7.

In the example shown in FIG. 33, the distribution concentration C of the contained atoms (Y) is from position t to position t. 1 (substantially zero here refers to the case where the amount is less than the detection limit; the meaning of "substantially zero" hereinafter is also the same) and gradually increases until it reaches Mt3a1. The density becomes C331, and a distribution state is formed in which the density takes a constant value c3o from position t, 3° to position t1.

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 tT, and reaches the concentration C841 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 CBB+ from the position ta to the position t361, and increases from the concentration CBB+ to the position t, 6. A distribution state is formed in which the concentration C1 is a constant value up to the position t7.

In the example shown in FIG. 36, the distribution concentration C of the contained atoms (Y) is from the position t to the concentration C36□
The concentration C1 increases linearly from
6, forming a distribution state.

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 oxygen atoms (0) (atoms belonging to Group Ⅰ of the periodic table (
Hereinafter abbreviated as "Group I atoms") will be used. Specific examples of the Group II atoms include B (boron), Al (aluminum), Ga (gallium), In (indium), and TI (thallium), with B, AI, and Ga being particularly preferred.

Specifically, the Group V atoms include P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc., with P and As being particularly preferred. Specific examples of the Group Ⅰ atoms include S (sulfur), Se (selenium), Te (tellurium), and Po (boronium), with S and Se being particularly preferred. In the present invention, the conductivity type and/or conductivity is mainly controlled by containing a group (I) atom, a group V atom, or a group (IV) atom as an atom (M) that controls conductivity in the layer region (M). It is possible to obtain the effect of controlling and/or the effect of improving the charge injection property between the layer region (M) and layer regions other than the layer region (M) of the upper layer. Atoms (M) that control conductivity contained in the layer region (M)
) content is preferably 1×10-” to 5×1
0' atom ppmN is more preferable than lXl0-''~IX
10' atomic ppm% is optimally lXl0 ~ 5xlO"
Preferably, it is expressed in atomic ppm. In particular, the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) described later in the layer region (M) is IX
In the case of 10" atomic ppm or less, the content of atoms (M) that controls conductivity contained in the layer region (M) is preferably 1 x 10" to 1 x 10 s atomic ppm. , the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) is 1xi
o'' atoms ppm, the content of atoms (M) that controls conductivity is preferably 1xlO-' to 5
It is desirable that the amount is xlO' atoms 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 9X
10' atomic ppm, more preferably lXl0' ~ 5x
lO' atoms p p m , optimally 1×102 to 3×1
It is desirable that the content be 0' atomic ppm. Especially when aiming for high dark resistance and/or high hardness, preferably 1×
It is desirable that the content be 10s to 9 x 105 atomic ppm,
When controlling spectral sensitivity, preferably 1 x 102 ~
Preferably it is 5 x 10' atomic ppm.

In the present invention, by containing germanium atoms (Ge) and/or tin or atoms (Sn) in the layer region (GS), it is possible to mainly control the spectral sensitivity, and in particular to use a semiconductor laser 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 such as. The content of germanium atoms (Ge) and/or tin atoms (S n ) contained in the layer region (GS) is preferably 1 to 9.5 x 10' atomic ppm, more preferably 1 x 10 to 8 x 10' atomic ppm. Atom 1) m% is optimally 5 x 10'' to 7 x 10' atoms 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 4X1.
It is desirable that the amount is 0.06 atomic ppm. In particular, the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) in the upper layer is 3X
In the case of less than 10' atomic ppm, the content of hydrogen atoms (H) or the sum of hydrogen atoms (H) and halogen atoms (X) is desirably 1 x 10'' to 4 x 10' 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 1xio" to 2X10' atomic ppm, and non-containing When composed of crystalline material, preferably l
It is desirable that the content be X104 to 7×10 B atoms ppm.

In the present invention, the upper layer composed of Non-8i (H, method, HRCVD method, and FOCVD method are preferred. These methods may be used in combination within the same device system.

For example, in order to form an upper layer composed of Non-8i (H, ) and/or an X supply gas that can supply halogen atoms (X), and atoms (
M supply gas capable of supplying 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 (0) A C supply gas capable of supplying a C supply gas, a Ge supply gas capable of supplying germanium atoms (Ge), and/or a Sn supply gas capable of supplying tin atoms (Sn) are placed in a deposition chamber in which the internal pressure can be reduced. A glow discharge is generated in the deposition chamber by introducing Non-8i (H) at a desired gas pressure onto the surface of a predetermined support that has been placed in a predetermined position and has a predetermined lower layer formed thereon.

A layer consisting of X) may be formed.

To form the upper layer composed of Non-3i (H, M 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 (0) and/or Ge supply gas and/or tin atoms (Sn) that can supply germanium atoms (Ge).
) 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-8i (H,
A layer consisting of X) may be formed.

To form the upper layer composed of Non-8i () (,
N supply gas capable of supplying H), M supply gas capable of supplying atoms (M) that control conductivity as necessary, and/or C supply gas capable of supplying carbon atoms (C), and /or N supply gas capable of supplying nitrogen atoms (N) and/or O supply gas capable of supplying oxygen atoms (0) and/or Ge supply gas capable of supplying germanium atoms (Ge) and/or A Sn supply gas that can supply tin atoms (S A gas is introduced into the deposition chamber at a desired gas pressure separately from the supply gas, and these gases are chemically reacted in the deposition chamber to form a predetermined lower layer that has been placed in a predetermined position in advance. A layer made of Non-8i (H,X) may be formed on the surface of the support.

In order to form the upper layer composed of No n-3i (H,
It may be formed by a known method described in Publication No. 2 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 (O), 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 SiH4,5izHzSisHs, 5i4
) II. Silicon hydride (silanes) in a gaseous state or that can be gasified are mentioned as those that can be effectively used, and SiH4,5i2Ha is also effective in terms of ease of handling during layer creation work and good Si supply efficiency. are listed as preferred. Further, these raw material gases for supplying Si may be diluted with gases such as Hz, He, Ar, Ne, etc., as necessary.

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 fluorine, chlorine, bromine, iodine element halogen gas, BrF, CIF, C1Fs, BrF
5, BrF5, IFs, IF
t + Interhalogen compounds such as ICI and IBr can be mentioned.

Specifically, silicon compounds containing a halogen atom, so-called silane derivatives substituted with a halogen atom, include, for example, S i F 4 , S t z F a , S
Preferred examples include silicon halides such as 1C14 and SiBr4.

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.

Moreover, 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, SiH, F, SiH2F2, 5iHFs, 5iHt
Is, 5iH2C12, S i HC1s, S
Gaseous or gasifiable substances such as halogen-substituted silicon hydrides such as i H2B r z and S i HBr5 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, S I H4, S 12 Ha.

S la Ha, S ia H+. This can also be carried out by causing a discharge by causing silicon hydride such as and silicon or a silicon compound for supplying Si to coexist in a deposition chamber.

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 raw materials for the introduction of Group II atoms, raw materials for the introduction of Group V atoms, or raw materials for the introduction of Group It is preferable to use materials that can be easily gasified under certain conditions.Specifically, as raw materials for introducing group Ⅰ atoms, B, H, etc. are used for introducing boron atoms.

B4H,,,B,H,,B,H,,,B,H,. ,B.

Boron hydride such as Hml B @ H1a, BF, BC
l.

Examples include boron halides such as BBrs. In addition,
AlCl5”, GaC15, Ga(CHs)m.

Mention may also be made of InC15, TlCl5, etc.

In the present invention, effective raw materials for introducing Group V atoms include PH,
Hydrogen ratio next to PIH, etc., PH, I.

PFs, PFs, PCIn, PCIB, PBr
s.

Examples include halogen north neighbors such as PBrs+ Pls. In addition, AsHs, AsF5, AsC15tAsBr
s, AsF5, 5bHs, Sb
Fm *5bFs *5bCIs! 5
bCIs, BiHs + BiCis,
B i B r s and the like can also be mentioned as effective starting materials for introducing Group V atoms.

Hydrogen sulfide (H2
S), SF4. SF6. SQ,,So,F2°CO8,CS,,CH,SH,C2H,SH.

Substances that are in a gaseous state or can be gasified, such as C, H, S, (CH,), S, (C, Ha), and S, may be mentioned. In addition, SeH*, 5eFa, (CHm)zSe, (Cz
Hs)z Se, TeHz, TeFs r(CH
Mention may be made of gaseous or gasifiable substances such as s )z Te+ (Cm Hs )2 Te.

In addition, a raw material for introducing atoms (M) to control these conductivities is Ha*He, Ar, etc. as necessary.

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

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 (0), 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, the saturated hydrocarbon is methane (CH,)
, ethane (Cm H,), propane (Cm H,).

H,), n-butane (nC4Hto), pentane (C,H,,), and ethylene hydrocarbons include ethylene (C,H,) and propylene (CjH,).

Butene-1 (C4Ha), Butene-2 (C4H8).

Isobutylene (C4Ha), Henna> (Cs H+
o).

Acetylene (C.

F2), methylacetylene (C,H,), butyne (C4
H, ), etc.

As a raw material gas containing St, C, and H as constituent atoms, S
Examples include alkyl silicides such as (CHI)41 St CC2H@)4.

In addition to this, CF, ,C(1,
, CHI CF, etc. (7) C7 hydrogenated carbon gases can be mentioned.

A raw material that can be effectively used as a raw material gas for introducing nitrogen atoms (N) is nitrogen (N, ) having N as a constituent atom or N and H as constituent atoms.
, ammonia (NH,), hydrazine (H, NNH,)
, hydrogen azide (HN,).

Mention may be made of gaseous or gasifiable nitrogen such as ammonium azide (NH,N, ), nitrogen compounds such as nitrides and azides. In addition, nitrogen atoms (N)
In addition to the introduction of halogen atoms (X), nitrogen trifluoride (pgN) and nitrogen tetrafluoride (F
, N, ) and the like 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 (NOa), -nitrogen dioxide (N,O).

Nitrogen sesquioxide (N20m), trinitrogen tetraoxide (N2
04), nitrogen sesquioxide (N, O,'), nitrogen dioxide (N
o, ), For example, disiloxane (Hl SiOS t Hs ) + trisiloxane (Ha St O8I F20S i Ha ) whose constituent atoms are a silicon atom (St), an oxygen atom (0), and a hydrogen atom (H).
Examples include lower siloxanes such as.

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 into the deposition chamber in a gaseous state together with other raw materials for forming the upper layer. Materials that can be used as raw materials for introducing germanium (Ge) or for introducing tin atoms (Sn) include materials that are gaseous at room temperature and pressure, or that can be easily gasified under at least layer-forming conditions. It is desirable that it be adopted.

As a material that can be a source gas for supplying Ge, GeH
t, Gez Ha, Ges Hs, Ge4H10
, Ges HI21 Ge6'H141Get H16
Germanium hydride in a gaseous state or that can be gasified, such as 1G e s Hll1 G e @ H2゜, is cited as one that can be effectively used, especially because of its ease of handling during layer creation work, good Ge supply efficiency, etc. At the point, GeH4
T G e z H@r G e s Hs is preferred.

In addition, GeHF, ,GeH,F, ,GeH.

F, GeHCl5, GeHa C1*, GeHsC
l, GeHBr5, GeHtBrs, GeHsB
r, GeHl*, GeHz rz, G
Hydrogenated germanium halides such as eHs I, GeF
4゜G e C a * G e B r a +
G e I 41 G e F x vGeC1*,
GeBr2. Examples include germanium halides such as GeIt.

As a substance that can be a source gas for supplying Sn, 5nH
a, Sni Ha, Sns Ha + 5n4H
lo+ S n5 Hll, 3 n6 HI3.
S n7 H+$1S n s H1,, S n *
Gaseous or gasifiable tin hydride such as H2i can be effectively used, and in particular, Sn H4+3n, H, , Sns H,, are listed as preferred.

In addition, 5nHFs, 5nHz F2, SnHmF
, 5nHCls r 5nHt C1* , 5nHs
C1, 5nHBrs, 5nHtBrs, 5nHs
Br, SnHI s , Snow I z , 5n
Hydrogenated tin halides such as Hs I, S n F4.
S n C14, SnBr4. Sni4. SnF*, 5
Gaseous or gasifiable substances such as tin halides such as nC1z, 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-3i having characteristics that 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 No n-3i (H,X) and hydrogen atoms (
H) and/or A- containing a halogen atom (X)
8i (hereinafter abbreviated as rA-8i (H,X) J)
When selecting and configuring, the support temperature (Ts) is
Although the optimum range is appropriately selected according to the layer design, it is usually desirable to set the temperature to 50 to 400°C, preferably 100 to 300°C.

The upper layer is Non-8i (H,X) and hydrogen atoms (H
) and/or polycrystalline silicon containing halogen atoms (X) (hereinafter referred to as rpo'1y-8i (H,X)J
When selecting and configuring a layer (abbreviated as ), there are various methods for forming the layer, including the following methods. One method is to set the support temperature at a high temperature, specifically 400 to 600°C, and deposit a film 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, Case 5x 10-' ~10W/
cm', preferably 5x10-' to 5W/cm3,
Optimally lXl0-”~2X10””W/c
It is desirable to set it to m”.

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.

1071.1072.107g, 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%, below [PH, /
(abbreviated as H, J) cylinder, 1075 is B, H, gas diluted with H, gas (purity 99°999%, hereinafter rB2
1076 is No gas (purity 9'9.9%) cylinder, 1077 is He gas (purity 99%).
．． 999%) cylinder, 1078 is a sealed container filled with AICII (99.99% purity).

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 1o15 of 01 is closed, and confirming that the outflow valves 1041 to 1047 and auxiliary valves 1o18 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 reads approximately 1X10-”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, and C from gas cylinder 1073.
H4 gas, PHs/H from gas cylinder 1074, gas,
B2 H6/H2 gas from gas cylinder 1o75, N from gas cylinder 1076, gas, 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 rA) passes through a closed container 1078 filled with lC1,
], /HeJ) are 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 SiHa gas, H, gas, AlC1,/He.
Gas was flowed into the deposition chamber 1001 through the gas discharge hole 1009 of the gas introduction pipe 1008. At this time, SiH4 gas flow rate is 50S CCM SHx gas flow rate is IO8CC
Each mass flow controller 1021, 1022, 1026° 1027 so that the MSNo gas flow rate is 58CCMSAIC1, /He gas flow rate is 1208CCM.
Adjusted with. The pressure inside the deposition chamber 1001 is 0.4 Tor
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 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 the lower part is placed on the cylindrical aluminum support. The formation of the layer was started. During the formation of the bottom layer, the SiHa gas flow rate was 503 CCM.

H so that the No gas flow rate is a constant flow rate of 58CCM.
2AlCl such that the gas flow rate increases at a constant rate from IO3CCM to 200SCCM.

/ The mass flow controllers 1021, 1022, 1026, 1027 were adjusted so that the He gas flow rate decreased at a constant rate from 120 SCCM to 40 SCCM, and the RF glow discharge was stopped when the lower layer with a layer thickness of 0.05 μm was formed. Outflow valve 1041, 1042, 1
046.1047 and auxiliary valve 1018 are closed;
The flow of gas into the deposition chamber 1001 was stopped, and the formation of the lower layer was completed.

Next, to form the first layer region of the upper layer, the outflow valves 1041 and 1042 and the auxiliary valve 1018 are gradually opened to supply SiH, gas, H, and gas to the gas inlet pipe 1008.
The gas was allowed to flow into the deposition chamber 1001 through the gas discharge hole 1009 . At this time, the SiH4 gas flow rate is 3008CCM
, H, and gas flow rates were adjusted to 3008 CCM using mass flow controllers 1021 and 1022, respectively. The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the pressure inside the deposition chamber 1001 was 0.5 Torr. After that, the power of the RF power supply (not shown) is
RF power is introduced into the deposition chamber 1001 through the high frequency matching box 1012 at a setting of 5 mW/cm'' to generate an RF glow discharge and begin forming the first layer region of the upper layer on the lower layer. , the RF glow discharge was stopped when the first layer region of the upper layer with a layer thickness of 20 μm was formed;
In addition, the outflow valves 1041 and 1042 and the auxiliary valve 1018 were closed to stop the gas from flowing into the deposition chamber 1001, and the formation of the first layer region of the upper layer was completed.

Next, to form the second layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened to supply 5iHa gas and CH4 gas to the gas introduction pipe 100.
8 into the deposition chamber 1001 through the gas discharge hole 1009. At this time, the S I Ha gas flow rate is 508CC
The MSCH and gas flow rates were adjusted to 500 SCCM using mass flow controllers 1021 and 1023, respectively. While checking the vacuum gauge 1017, adjust the pressure inside the deposition chamber 1001 to 0.4 Torr by turning the main valve 101.
Adjusted the aperture of 6. 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 region of the upper layer is After forming the second layer region of the upper layer with a layer thickness of 0.5 μm, the RF glow discharge is stopped, and the outflow valves 1041 and 1043 and the auxiliary valve 1018 are closed. Then, the flow of gas into the deposition chamber 1001 was stopped, and the formation of the second layer region of the upper layer was completed.

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

It goes without saying that the outflow valves for gases other than those necessary for forming each layer are completely closed, and each gas is not allowed to flow through the deposition chamber 1001 or the 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.

Further, 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 H, gas, and No 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. The electrophotographic properties were checked.

When comparing the number of spots as an image characteristic, it was found that
．． The electrophotographic light-receiving member of Example 1 was 3/3 of the number of spots of 1 mm or less than the electrophotographic light-receiving member of Comparative Example.
It turned out that the number of points was 4 or less. moreover,
In order to compare the degree of roughness, a diameter of 0.05 mm was used.
The image density was measured at 100 points with a circular area as one unit, and the variation in image density was evaluated. 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 superior to the electrophotographic light receiving member of Comparative Example.

<Example 2> An electrophotographic light-receiving member was produced in the same manner as in Example 1 by changing the way the A I C1s/He gas flow rate was changed in the lower layer of Example 1 and using the production conditions shown in Table 3. ,
Similar evaluations were conducted, and as in Example 1, good effects were obtained in improving the edges, 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 (
Change the H2 gas to a No gas (purity 99.9%) cylinder in the upper layer,
In the upper layer, He gas, He gas, N, gas, AlC
An electrophotographic light-receiving member was prepared in the same manner as in Example 1 using 1,/He gas and B, H, /H gas under the preparation conditions shown in Table 5, and the same evaluation was performed. Example 1
Similar to the above, good effects were obtained in improving burrs, roughness, and layer peeling.

<Example 5> In Example 1, P Hs / H = gas cylinder was
Change to gas (purity 99.9999%) cylinder, B, H,
/H, gas cylinder NH, gas (purity 99.999%)
A light-receiving member for electrophotography was produced in the same manner as in Example 1 using the production conditions shown in Table 6, except that the H gas was replaced with Ar gas and the CH gas was replaced with NH gas in the upper layer. Similar evaluations were conducted, and as in Example 1, good effects were obtained in improving the edges, roughness, and layer peeling.

<Example 6> PH, /H, gas is further used in the upper layer, and the seventh
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 7> In the upper layer of Example 1, B* Ha /Hz and S I F m gas (not shown) (purity 99.999%) were further used, and Example 1 was prepared according to the production conditions shown in Table 8. An electrophotographic light-receiving member was prepared in the same manner as in Example 1, and the same evaluation was performed. As in Example 1, good effects were obtained in improving the edges, roughness, and layer peeling.

<Example 8> An electrophotographic light-receiving member was produced in the same manner as in Example 1, using PH, /H, gas, N, and gas in the upper layer and according to the production conditions shown in Table 9. As a result of the evaluation, as in Example 1, good effects were obtained in improving porousness, roughness, and layer peeling.

<Example 9> In Example 1, the CH, gas cylinder was changed to a C, H2 gas cylinder (purity 99.9999%), the N, gas cylinder was changed to a No gas cylinder, and the CH, gas was changed to a C, H, gas cylinder in the upper layer. 10th using additional NO gas.
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 10) An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 11, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 11> In Example 1, the PH, /H, gas cylinders were changed to NH, gas (purity 99.999%) cylinders, and the CH4 gas was changed to NHs gas in the upper layer, and according to the production conditions shown in Table 12. A light-receiving member for electrophotography was prepared in the same manner as in Example 1, and the same evaluation was performed. As in Example 1, good effects were obtained in improving marks, roughness, and layer peeling. .

<Example 12> An electrophotographic light-receiving member was produced in the same manner as in Example 6, using SiF4 gas in the upper layer of Example 6, and under the production conditions shown in Table 13, and the same evaluation was performed. However, similar to Example 6, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 13> An electrophotographic light-receiving member was produced in the same manner as in Example 9, using B2H, /H2 gas and 5ixH, gas in the upper layer and according to the production conditions shown in Table 14, and the same evaluation was carried out. When this was carried out, similar to Example 9, there were no spots, roughness, or roughness.
A good effect on layer peeling was obtained.

<Example 14> Further using pH, /H, gas in the upper layer, the first
An electrophotographic light-receiving member was produced in the same manner as in Example 11 under the production conditions shown in Table 5, and the same evaluation was performed.
Similar to Example 11, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 15> In Example 1, B2 Ha /H! Ge gas cylinder
An electrophotographic light-receiving member was produced in the same manner as in Example 1, using G e Hm gas in the upper layer instead of the H4 gas (purity 99°999%) cylinder, and according to the production conditions shown in Table 16. Similar evaluations were conducted, and as in Example 1, good effects were obtained in improving the edges, roughness, and layer peeling.

<Example 16) In Example 1, the outer diameter of the cylindrical aluminum support was 80 mm, and an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production 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, there were improvements in marks, roughness, and layer peeling. Good effects were obtained.

<Example 17> In Example 1, the outer diameter of the cylindrical aluminum support was set to 60 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 18. Evaluations were conducted in the same manner as in Example 1, except that an electrophotographic device modified from a copying machine NP-1502 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 produced in the same manner as in Example 1 under the production 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 to improve the appearance of edges, roughness, and layer peeling.

<Example 19> In Example 1, the outer diameter of the cylindrical aluminum support was set to 15 mm, and an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 20. Evaluations were carried out in the same manner as in Example 1, except that an electrophotographic apparatus prototyped in 1 was used, and as in Example 1, good effects were obtained in improving marks, 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-3i (H, 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, B, H
6/H, a S I Fa gas cylinder was used instead of the 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, drain valve 1
041, 1042, 1044, 1046, 1047 and auxiliary valve 1018 to gradually open SiH4 gas, H
2 gas, PH3/H, gas, No gas, AlCl, /H
E-gas was flowed into the plasma generation region 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, S I H4 gas flow rate is 150SCCM1H, gas flow rate is 20SCCMSNo gas flow rate is IO8CCMSPH
, /H, gas is 1.58CCM, A I C1, /He
Each mass flow controller 1021, 1022, 1024, 10 so that the gas flow rate is 400SCCM
Adjusted with 26.1027. 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 a μW power source (not shown) is set to 0.5 W/cm', and μW power is introduced into the plasma generation region 1109 through the waveguide 1103 and the dielectric window 1102 to generate μW glow discharge. Formation of the lower layer on the support 1107 was started. During the formation of the bottom layer, SiH4
Gas flow rate is 150SCCM, No gas flow rate is IO3CC
M, PH, /H, gas flow rate is constant flow rate of 1.58 CCM, H2 gas flow rate is 500 SCCM from 20 SCCM.
AlC1,/ so as to increase at a constant rate in SCCM
The He gas flow rate is 400 SCC at 0.01 μm on the support side.
In order to decrease from M to soscCM at a constant rate, from 80SCcm to 5osccM at 0.01 μm on the upper layer side.
Mass flow controller 1021.1022, 1024, 1026.1027 so that it decreases at a constant rate.
When the lower layer with a thickness of 0.02 μm was formed, the μW glow discharge was stopped, and the outflow valve 1041,
1042, 1044° 1047 and auxiliary valve 1o1
8 was closed to stop the flow of gas into the plasma generation region 1109, 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, 1045 and the auxiliary valve 10
Gradually open 18 and add SiH4 gas, H2 gas, SiF4
was caused to flow into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 111o. At this time, Si
H, gas flow 41 (700SCCMSH, gas flow rate 50
0SCCM, S I F 4 gas flow rate is 303CCM
Each mass flow controller 1021
Adjusted at 1022.1025. The pressure inside the deposition chamber 11o1 was adjusted to 0.5 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 chamber 1109 in the same manner as the lower layer, and the first layer region of the upper layer is formed on the lower layer. Formation was started, and a first layer region of the upper layer having a layer thickness of 20 μm was formed.

Next, to form the second layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened to supply SiH, gas, and CH4 gas to the gas inlet pipe 111.
Plasma generation space 11 through gas discharge holes (not shown)
09. At this time, the SiHa gas flow rate is 15
0SCCM.

Each mass flow controller 1021 and 1023 was adjusted so that the CH4 gas flow rate was 500 SCCM. The pressure inside the deposition chamber 1101 was 0.3 mTorr. After that, the power of the μW power supply (not shown) was increased to 0.5W/cm"
was set to generate μW glow discharge in the plasma generation region 1109, and a second layer region of the upper layer having a layer thickness of 1 μm was formed on the first layer region of the upper layer.

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.

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 [Effects of the Invention] By making the electrophotographic light-receiving member of the present invention have the specific layer structure as described above, the light-receiving member made of A-8i. It can solve all the problems with conventional light-receiving members for electrophotography, and has particularly excellent electrical properties, optical properties,
Indicates photoconductive properties, image properties, durability and use environment properties.

In particular, in the present invention, aluminum atoms (AI), silicon atoms (St), and especially hydrogen atoms (H) are contained in the lower layer in a non-uniform distribution state in the layer thickness direction, and atoms ( By containing CNO6), the electric charge between the aluminum support and the upper layer (
The injection properties of the photo carrier (photo carrier) are improved, and the structural continuity of the constituent elements between the aluminum-based support and the upper layer is improved, so image characteristics such as roughness and edges are improved, and half- High-quality images with clear tones and 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 3i (H,
It is possible to alleviate the stress caused by the difference in the thermal expansion coefficient of the 3i (H, can.

[Brief explanation of drawings]

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 states of c), respectively, for silicon atoms (S i ) contained in the lower layer,
Hydrogen atom (H), atom that adjusts durability (CNOC)
, an explanatory diagram of the distribution state of atoms (Mc) that adjust the image quality contained in the upper layer if necessary, and FIGS. 17 to 36 respectively show atoms (M) that control conductivity and carbon atoms ( C) and/
or nitrogen atom (N) and/or oxygen atom (0),
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-8i...Free surface In Fig. 37, 1000...Deposition device 1001 by RF glow discharge decomposition method...Deposition chamber 1005...Cylindrical 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; A light-receiving member comprising an upper layer made of a non-single-crystalline material containing at least one of atoms and halogen atoms. (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.