JPS63276060A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To improve overall characteristics by consisting a photoreceptive layer, successively from a base side, of a lower layer which has the part contg. an aluminum atom, silicon atom and hydrogen atom in the distribution state nonuniform in the layer thickness direction and an upper layer which contains at atom to control conductivity in the layer region in contact with the lower layer. CONSTITUTION:This photoreceptive member 10 has the photoreceptive layer 102 having the layer constitution consisting of the lower layer 103 which is constituted of AlSiH and has the part contg. the aluminum atom (Al), the silicon atom (Si) and the hydrogen atom (H) in the distribution state nonuniform in the layer thickness direction and the upper layer 104 which is constituted of Non-Si(H, X) and contains the atom (M) to control the conductivity in the layer region in contact with the lower layer 103 on an aluminum base 101. The upper layer 104 has a free surface 105. Particularly the photoconductive characteristics, image characteristics, durability and use environment characteristics are thereby obtd.

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-8i) is a photoconductive material that has recently attracted attention.
855718 and the like describes its application as a light-receiving member for electrophotography. FIG. 2 is a sectional view schematically showing the layer structure of a conventional light-receiving member for electrophotography.
1 is an aluminum support, and 202 is a photosensitive layer made of A-3i.

Such electrophotographic light-receiving members are generally produced by heating an aluminum support 201 to 50°C to 350°C, and forming a film on the support by vapor deposition, thermal CVD, plasma CVD, sputtering, or the like. Photosensitive layer 2 made of A-8i
Create 02.

However, in this electrophotographic ambient light receiving member, since the thermal expansion coefficients of aluminum and A-3i differ by about one order of magnitude, cracks or peeling may occur in the A-3i negative light 202 during cooling after film formation. This has become a problem. In order to solve these problems, JP-A-59-28162 proposes an electrophotographic photoreceptor consisting of an aluminum support, an intermediate layer containing at least aluminum, and an A-8i photoreceptor. The intermediate layer containing at least aluminum alleviates the stress caused by the difference in thermal expansion coefficient between the aluminum support and the A-3i photosensitive material.
A-8i Reduces cracks and peeling caused by bad exposure.

[Problem that the invention seeks to solve]

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

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

In particular, as a result of improved image resolution, there is a reduction in non-uniformity in fine areas of image density, commonly called "roughness", and a reduction in image defects in the form of black or white dots, commonly called "boke". 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, Image defects and A-
There was a problem that the durability of the electrophotographic light-receiving member was impaired due to the occurrence of peeling of the 8i film.

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

Therefore, while efforts are being made to improve the properties of the A-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 is made of an inorganic material (hereinafter referred to as rA
1siHJ), and the aluminum atom (AI), silicon atom (SL), and hydrogen atom (I
A lower layer having a portion containing I) in a non-uniform distribution state in the layer thickness direction, and a silicon atom (Si) as a base material, and at least one of a hydrogen atom (H) and a halogen atom (X). (hereinafter referred to as rNo)
n-3i (abbreviated as H,

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. , image characteristics, durability and use environment characteristics.

In particular, by containing aluminum atoms (A1), silicon atoms (Si), and especially hydrogen atoms (H) in a non-uniform distribution state in the layer thickness direction in the lower layer, the relationship 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, 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 can alleviate the stress caused by the difference in thermal expansion coefficient of the (H, .

In particular, in the present invention, halogen atoms (X) in the lower layer
By including silicon atoms (Si), aluminum atoms (A1), etc., it is possible to compensate for the dangling bonds and obtain a more stable state in terms of the organizational structure. Coupled with the effects due to the distribution of Al) and hydrogen atoms (H), this method is characterized by a remarkable improvement in image characteristics such as roughness and edges.

Furthermore, in the present invention, by containing atoms (M) that control conductivity in the layer region in contact with the lower layer in the upper layer, charge injection properties or charge injection blocking properties between the upper layer and the lower layer are achieved. It is possible to selectively control or improve image characteristics such as roughness and spots, and it is possible to stably and repeatedly produce high-quality images with clear halftones and high resolution. charging ability,
Sensitivity and durability are also improved.

In addition, the above-mentioned Japanese Patent Application Laid-Open No. 59-28162 describes that aluminum atoms (A1) and silicon atoms (Si) are contained nonuniformly in the layer thickness direction, and further hydrogen atoms ()l) are contained. Although it is mentioned, there is no mention of how hydrogen atoms are contained, and it is clearly distinguished from the present invention.

[Detailed description of the invention]

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

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

The electrophotographic light-receiving member 100 shown in FIG. 1 is made of Al5iH on an aluminum-based support 101 for electrophotographic light-receiving members, and the aluminum atoms (AI) and silicon atoms (Si) Hydrogen atom (H) is
Consisting of a lower layer 103 having a portion containing non-uniform distribution in the layer thickness direction, and Non-3i (H,X),
In addition, the photoreceptor layer 102 has a layer structure including an upper layer 104 containing atoms (M) for controlling conductivity in a layer region in contact with the lower layer. Top layer 104 has a free surface 105.

! Aluminum support 101 used in the present invention
An aluminum alloy is used as the material. This invention. There are no particular restrictions on the alloy components, including the substrate aluminum, in the aluminum alloy (the type and composition of the components can be selected arbitrarily). (J
IS), AA standards, BS standards, DIN standards, international alloy registration, etc., for pure aluminum, Al-Cu, etc., which are standardized or registered as wrought materials, castings, die castings, etc.
Al-In series, Al-3i series, Al-Mg series, Al-M
Alloys with compositions such as g-8i series, Al-Zn-Mg series, etc.
-Cu-Mg system (duralumin, similar duralumin, etc.),
Al-Cu-8i system (Rautal etc.), Al-Cu-N
Contains i-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 0105~0
．． 20% by weight, Mn O, 05% by weight or less, Zn
0.10% by weight or less, At 99.00% by weight or more.

As the A1-Cu-Mg system, for example, Moon 52017, SiO, 05 to 0.20% by weight, Fe 0.7% by weight
Below, Cu3.5~4.5% by weight, Mn 0.40~
1.0% by weight, MgO, 40-0.8% by weight, Zn
O, 25% by weight or less, Cr00, 10% by weight or less, Al
The remainder is mentioned.

As the ^l-Mn system, for example, JIS3003, Si
0.6% by weight or less, Fe 017% by weight or less, Cu
Examples include O, 05 to 0.20% by weight, Mn 1.0 to 1.5% by weight, ZnO, 10% by weight or less, and the balance A1.

As the Al-3i system, for example, Jl54032, 5
i11.0 to 13.5% by weight, Fe1.0% by weight or less,
CuO, 50-1.3% by weight, MgO, 8-1.3
Weight%, Zn 0.25% by weight or less, CrO,1
0% by weight or less, NiO, 5-1.3% by weight, AI
The remainder is mentioned.

As the Al-Mg system, for example, JIS 5086, S
i0.40 total amount % or less, Fe O, 50 weight% or less,
CuO, 10% by weight or less, Mn 0.20-0.
7% by weight, Mg 3.5-4.5% by weight, Zn 0.2
5% by weight or less, CrO, 05-0.25% by weight, Ti0
．． 15% by weight or less, the remainder being A1.

Furthermore, Si Q, 50% by weight or less, Fe O,
25% by weight or less, CuO, 04-0.20% by weight,
In 0.01-1.0% by weight, Mg 015-10
Weight%, Zn 0.03 to 0.25% by weight or less, Cr
O, 05-0.50% by weight, Ti or Tr O,
05 to 0.20% by weight, tt, 1.0 cc or less per Attoo gram, and the remainder At.

Furthermore, St O, 12% by weight or less, Fe0
0.015% by weight or less, Mn 0.30% by weight or less, Mg
0.5-5.5 wt%, Zn Q, 01-1.0 wt% or less, Cr0120 wt% or less, Zr O, 01-
0.25% by weight or less, the balance being A1.

As the Al-Mg-3t system, for example, JIS6063, Sin, 20 to 0.6% by weight, FeO, 35% by weight or less, CuO, 910% by weight or less, In 0.10
Weight% or less, MgO, 45-0.9% by weight, Zn
0.10% by weight or less, CrO, 10% by weight or less,
Examples include TiO, 10% by weight or less, and the balance Al.

As the Al-Zn-Mg system, for example, JIS7NO1, St O, 30% by weight or less, Fe O, 35% by weight
Below, CuO0 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, CrO, 30% by weight or less, Ti
0.20% by weight or less, Zr O, 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 have a cylindrical shape or a plate-like endless belt shape with a smooth surface or an uneven surface, and its thickness is determined as appropriate so as 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 caused by a plurality of 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.

1 Ri 1 The lower layer in the present invention is composed of an inorganic material containing at least aluminum atoms (Al), silicon atoms (Si), hydrogen atoms (H), and halogen atoms (X) as constituent elements, and is made of an inorganic material containing at least aluminum atoms (Al), silicon atoms (Si), hydrogen atoms (H), and halogen atoms (X), and has durability as required. Atom that adjusts gender (CNOc)
, may contain atoms (M c ) that adjust image quality.

Aluminum atoms (A1), silicon atoms (S i), and hydrogen atoms (H) contained in the lower layer are uniform throughout the entire layer area of the lower layer (although they are contained, they are not concentrated in the layer thickness direction). The distribution concentration is uneven in some parts.However, in the in-plane direction parallel to the surface of the support, it is uniformly distributed and has no bias (its inclusion makes the properties uniform in the in-plane direction). It is also necessary from the perspective of achieving this goal.

The halogen atoms (X) contained in the lower layer, the atoms that adjust the durability (CNOC) and the atoms that adjust the image quality (Mc) contained as necessary are uniformly distributed throughout the entire layer area of the lower layer. It may be contained in a uniformly distributed state, or it may be contained uniformly in the entire layer area of the lower layer (it may be contained, but it may be contained in a non-uniformly distributed state in the layer thickness direction). However, in any case, in the in-plane direction parallel to the surface of the support, it is uniformly distributed and without bias (the inclusion of the material helps to make the properties uniform in the in-plane direction). It is also necessary from the perspective of achieving this goal.

Further, in one of the preferred embodiments, aluminum atoms (AI), silicon atoms (
The distribution state of aluminum atoms (AI), silicon atoms (Si), and hydrogen atoms (H) are continuous and evenly distributed in the entire layer area, and the distribution state of aluminum atoms (A1) is uniform. The distribution concentration in the layer thickness direction decreases from the support side toward the upper layer, and silicon atoms (Si
), the distribution concentration of hydrogen atoms (H) in the layer thickness direction increases from the support side toward the upper layer, so the affinity between the aluminum support and the lower layer and between the lower layer and the upper layer is improved. Excellent.

In the electrophotographic light-receiving member of the present invention, as described above, aluminum atoms (At) 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 halogen atom (X), an atom that adjusts durability (CNOc) contained as necessary, and an atom that adjusts image quality (Me) are shown in a typical example of the distribution state in the layer thickness direction.

In Figures 3 to 8, the horizontal axis is the aluminum atom (
AI) (hereinafter abbreviated as "Atom (Al) J"), halogen atom (X) (hereinafter abbreviated as "Atom (X)"), durability adjusting atom (CNOc) (hereinafter "Atom (CNO)")
c) Atom (Me), which adjusts the image quality (hereinafter abbreviated as "Atom (Mc)J", Atom (AI) and Atom (X)
, atom (CNOc), and atom (Mc) are collectively referred to as [atom (AX)J]. However, atoms (AI) and atoms (X
), the distribution state of atoms (CNOc) and atoms (Mc) in the layer thickness direction may be the same or different), the vertical axis indicates the layer thickness of the lower layer, t, indicates the position of the end surface of the lower layer on the support side, and t□ indicates the position of the end surface of the lower layer on the upper layer side. That is, the lower layer containing atoms (AX) is 1. layered towards the sides.

FIG. 3 shows a first typical example of the distribution state of atoms (AX) 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 (AX) takes a constant value of concentration C□ from position t to position t□, and from position [81 to position tA. A distribution state is formed in which the concentration decreases linearly from the concentration C11 until the concentration reaches 0.2 at the position t7.

In the example shown in FIG. 4, the distribution concentration C of the contained atoms (AX) varies from position tB to position t. Concentration C4 until
The concentration C decreases linearly from 1 at position 11.
42 is formed.

In the example shown in FIG. 5, the distribution concentration C of the contained atoms (AX) is the concentration C6 from the position to to the position t7.
A distribution state is formed in which the concentration gradually and continuously decreases from 1 to reach the concentration CI2 at the position t7.

In the example shown in FIG. 6, the distribution concentration C of the contained atoms (AX) is the concentration Cf from position tll to position t61.
It takes a constant value it, and from position tel to position ta, the concentration decreases from C6 to -order number, forming a distribution state in which the concentration becomes Cas at position t7.

In the example shown in FIG. 7, the distribution concentration C of the contained atoms (AX) takes a constant value of concentration C71 from position t to position 11+, and from position t71 to position 11, the distribution concentration C takes a constant value of concentration C71. A distribution state is formed in which the concentration gradually and continuously decreases to a concentration C73 at position t7.

In the example shown in FIG. 8, the distribution concentration C of the contained atoms (AX) is 0.1 from position t8 to position t1.
The concentration C gradually and continuously decreases from t to t7.
A distribution state is formed such that at.

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,
It contains silicon atoms (S i) and hydrogen atoms (H), and has a portion with a high distribution concentration C of atoms (A1), and has an interface 1
In No. 1, a preferable example is formed when the distribution concentration C has a portion where it is considerably lower than that on the support side. In this case, the maximum value Cma of the distribution concentration of atoms (A1)
It is desirable that x be formed in a layer such that the distribution state of x is preferably 10 atomic % or more, more preferably 30 atomic % or more, and optimally 50 atomic % or more.

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

9 to 16 show silicon atoms (Si) contained in the lower layer of the electrophotographic light receiving member of the present invention.
, hydrogen atoms (H), halogen atoms (X), atoms contained as needed (CNOc), and atoms (M c ) in the layer thickness direction.

In FIGS. 9 to 16, the horizontal axis represents silicon atoms (St
), hydrogen atom (H), halogen atom (X), atom (CNOc
), atoms (Mc) (hereinafter these will be collectively referred to as [atoms (S
HX) Abbreviated as J. However, silicon atoms (Si), hydrogen atoms (H), atoms (X), atoms (CNOc), and atoms (M
The distribution state of c) in the layer thickness direction may be the same or different. tT indicates the position of the end face of the lower layer on the upper layer side. That is, the lower layer containing atoms (SHX) is formed from the ts side toward the 11 side.

FIG. 9 shows a first typical example of the distribution state of atoms (SHX) 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 (SHX) increases numerically for one hour from the concentration 0.1 from position t to position tl11, and from position t91 to position 11. Until then, a distribution state is formed that takes a constant value of concentration C9.

In the example shown in FIG. 10, the atoms contained (SHX)
The distribution concentration C is the concentration C from position 1++ to position 11.
A distribution state is formed in which the concentration increases linearly from 0.degree. 1 and reaches the concentration C+o* at position t7.

In the example shown in FIG. 11, the atoms contained (SHX)
The distributed concentration C gradually and continuously increases from the concentration Cl1l from the position t to the position t7, and forms a distribution state in which the concentration C11 is reached at the position 1T.

In the example shown in FIG. 12, the atoms contained (SHX)
The distribution concentration C increases numerically for one hour from the concentration CIll from the position ta to the position t12+, and then reaches the position i +2
1, the concentration becomes CI22, and the position t,. From 1 to position tT, a distribution state is formed in which the concentration C1ffil is a constant value.

In the example shown in FIG. 13, the atoms contained (SHX)
The distribution concentration C gradually and continuously increases from the concentration Ctsl to the position tIll until it reaches the position tIll.
A distribution state is formed in which the concentration is C13 at 11, and the concentration C1,3 is a constant value from position t1□ to position t7.

In the example shown in FIG. 14, the contained atoms (SHX)
The distribution concentration C gradually and continuously increases from the concentration CI41 from the position t8 to the position t7, and forms a distribution state in which the concentration CI4□ is reached at the position t7.

In the example shown in FIG. 15, one atom contained (SHX
) distribution concentration C is substantially zero from position ts to position t+11+ (here, substantially zero means the case where the amount is below the detection limit; the meaning of "substantially zero" hereinafter is also the same). concentration C36 at position t1□.
, and the position t15. Concentration C until reaching position 1T
A distribution state is formed that takes a constant value of 362.

In the example shown in FIG. 16, the atoms contained (SHX)
The distribution concentration C gradually increases from substantially zero from position t to position jt, and reaches the concentration CI8 at position ta.
A distribution state is formed in which the number is 1.

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, contains aluminum atoms (A1) and has a low distribution concentration C of silicon atoms (Si) and hydrogen atoms (H) on the support side, and at the interface 11, the distribution concentration C is low on the support side. A preferred example is formed in the case where the lower layer is provided with a distribution of silicon atoms (S i ) and hydrogen atoms (H) having a considerably elevated portion. In this case, the maximum value Cwax of the distribution concentration of the sum of silicon atoms (Si) and hydrogen atoms (H) is preferably 10 atom % or more, more preferably 30 atom % or more,
It is desirable that the layer be formed in such a way that it can optimally have a distribution state of 50 at % 4 or more.

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

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

As the halogen atom (X), a fluorine atom (F),
Chlorine atom (CI), bromine atom (Br), iodine atom (I
) is used. In the present invention, mainly by containing a fluorine atom (F) and/or a chlorine atom (CI) and/or a bromine atom (Br) and/or an iodine atom (1) as a halogen atom (X) in the lower layer, It is possible to compensate for dangling bonds of silicon atoms (Si), aluminum atoms (AI), etc. contained in the lower layer, thereby making it structurally stable and improving the layer quality. The content of halogen atoms (X) contained in the lower layer is determined as desired so as to effectively achieve the object of the present invention, but preferably 1X4X10' atoms 1
)1) mN, preferably 10 to 3X10' atoms ppm
% Optimally, it is desirable that 1X10'' to 2X10'2X10' atoms be 9.

Atoms (M
As for c), atoms belonging to group Ⅰ of the periodic table (hereinafter abbreviated as ``group Ⅰ atoms''), atoms belonging to group V of the periodic table excluding nitrogen atoms (hereinafter referred to as ``group V atoms'') are ''), atoms belonging to Group VI of the periodic table (hereinafter abbreviated as "Group v1 atoms") excluding oxygen atoms (0) are used. Part ■
Specifically, the group atoms include B (boron), AI (aluminum), Ga (gallium), and In (indium).

Examples include TI (thallium), and B, AI, and Ga are particularly preferred. Specifically, the Group V atoms include P (phosphorus),
As (arsenic), sb (antimony), Bi (bismuth)
etc., with P and As being particularly suitable. Specifically, Group VI atoms include S (sulfur), Se (selenium), Te
(tellurium).

Examples include Po (polonium), and S and Se are particularly preferred. In the present invention, atoms (
Mc) as a group II atom or a group V atom or a group VI atom
By containing the group atoms, it is possible to mainly obtain the effect of improving the charge injection property between the aluminum-based support and the upper layer and/or the effect of improving the charge migration property in the lower layer. Furthermore, 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 (Mc) that adjusts the image quality contained in the lower layer is preferably lXl0-"~5
X10' atom 1) 9m% more preferably 1xlO-"
~1xlO' atoms 1) pm % optimally lXl0-'
~5X10'' atomic ppm is preferred.

In the present invention, the lower layer composed of Al5iH is formed, for example, by the same vacuum deposition film forming method as the upper layer described later, with numerical conditions of film forming parameters set appropriately so as to obtain desired characteristics. Ru. Specifically, for example, glow discharge method (alternating current discharge CVD such as low frequency CVD, high frequency CVD or microwave CVD, or direct current discharge CVD), ECR-CVD method, sputtering method,
Vacuum evaporation method, ion blating method, photoCVD method, activated species (
A) and an active species (B) generated from a film-forming chemical that chemically interacts with the active species (A), respectively, in a film-forming space for forming a deposited film. A method of forming a material by introducing and chemically reacting them (hereinafter abbreviated as "rHRCVD method"), a raw material gas of the material,
A method of forming a material by introducing a halogen-based oxidizing gas that has the property of oxidizing the raw material gas into the amount of the film to be deposited separately and causing a chemical reaction between them (hereinafter referred to as rFOcVD). 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, an ion blating method, an HRRCVD method, and a FOCVD method are suitable. These methods may be used in combination within the same device system. For example, in order to form a lower layer composed of Al5iH by the glow discharge method, basically a raw material gas for supplying aluminum atoms (AI) and a raw material gas for supplying silicon atoms (S
i) and a hydrogen atom (H)
H supply gas that can supply halogen atoms (X), X supply gas that can supply halogen atoms (X), and CN0c supply gas that can supply atoms (CNOC) that adjust durability as necessary
A Me supply gas capable of supplying atoms (M c ) for adjusting image quality as necessary is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated within the deposition chamber. , a layer made of Al5iH may be formed on the surface of a predetermined support that has been placed in a predetermined position in advance.

In order to form a lower layer composed of Al5iH by the HRCVD method, basically a raw material gas for supplying A1 that can supply aluminum atoms (AI) and a silicon atom (S
i) and a halogen atom (X
), a CN0c supply gas that can supply atoms (CNOC) that adjust the durability as necessary, and atoms (M c ) that adjust the image quality as necessary.
Separately, if necessary, Me supply gas capable of supplying
Alternatively, at the same time, the gas may be introduced at a desired pressure into the activation space provided at the front stage of the deposition chamber, the interior of which can be reduced in pressure, to generate a glow discharge or heat the activation space. to generate active species (A) and hydrogen atoms (H
) is similarly introduced into another activation space to generate active species (B), and the active species (A) and active species (B) are separately introduced into the deposition chamber. A layer made of Al5iH may be formed on the surface of a predetermined support by introducing the Al5iH into a predetermined position.

In order to form the lower layer composed of Al5iH by the FOCVD method, basically a raw material gas for supplying aluminum atoms (AI) and a silicon atom (S
i), a H supply gas that can supply hydrogen atoms (H), and an X supply gas that can supply halogen atoms (X), and adjust the durability as necessary. a CN0c supply gas capable of supplying atoms (CNOc);
A Mc supply gas capable of supplying atoms (Mc) for adjusting image quality as necessary may be supplied separately or -
At the same time, a halogen (X) gas is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a halogen (X) gas is introduced into the deposition chamber at a desired gas pressure separately from the source gas. By chemically reacting the gas of
A layer consisting of H may be formed.

When forming by sputtering method, for example, Ar5
A target made of A1, S in an atmosphere of an inert gas such as He or a mixed gas based on these gases.
using a target composed of t or Al and S
Hydrogen atoms (H) using a mixed target of t
Raw material gas for H supply and halogen atom (X) that can supply
X supply gas that can supply X, CN0c supply gas that can supply atoms (CNOc) that adjust durability as necessary, and atoms (M c ) that adjust image quality as necessary Mc supply gas is introduced into the deposition chamber for sputtering, and if necessary, aluminum atoms (A
1) A raw material gas for AI supply that can supply and/or a Si supply gas that can supply silicon atoms (Si),
This is accomplished by introducing the gas into a deposition chamber for sputtering and forming a plasma atmosphere of the desired gas.

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 (Al), silicon atoms (Si) contained in the layer,
Hydrogen atoms (H), halogen atoms (X), atoms that adjust durability (CNOc) contained as necessary, and atoms that adjust image quality (Me) (hereinafter these will be collectively referred to as [
By changing the distribution concentration C of atoms (AsH) (abbreviated as J) in the layer thickness direction, a desired distribution state in the layer thickness direction (depth
In order to form a layer with profile), in the case of glow discharge method, HRCVD method, and FOCVD method, the raw material gas for atomic (ASH) supply whose distribution concentration should be changed, and the gas flow rate changed as desired. This is accomplished by changing the rate appropriately according to the rate curve and introducing it into the deposition chamber.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system is 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 Al 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 raw material gas for A1 supply used in the present invention include A I CI H, A I B r
s.

AI 1. , AI (CH,), CI, AI (CH,
),.

AI C0CH,)a, AI (C, Hs),
.

AI(OC*Ha)s, AI(i-
C4He)s +AI (i Cm Hy)s+ A
I (Cs Ht )s.

AI (QC, H,), etc. can be cited as examples of methods that can be effectively used. In addition, these raw material gases for A1 supply are converted into H* + He * A r T N as necessary.
It may be used after being diluted with a gas such as e.

Substances that can be used as raw material gas for supplying Si used in the present invention include Si Ha and S t x Ha.

StsHm, 5t4Ht. Silicon hydride (silanes) in a gaseous state or that can be gasified, such as
5iHa and 5itHs are preferred in terms of i supply efficiency. In addition, these raw material gases for supplying Si may be converted to Hz −He or Ar + as necessary.
It may be used after being diluted with a gas such as Ne.

Effective halogen supply gases used in the present invention include poly(halogen compounds), such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, and other gaseous or gasified halogen compounds. Preferred examples include halogen compounds.

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.

Examples of halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, B r F, CIF, and CIF s.

BrF* *BrF5 l IFs w IF
Interhalogen compounds such as 7 + I CI+IBr can be mentioned.

Examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include SiF4. Preferred examples include silicon halides such as Six Fs and 5iC14°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 without using halogen atoms, a lower layer consisting of Al5iH/ can be formed on a desired support.

When forming a lower layer containing halogen atoms according to the glow discharge method or HRCVD method, basically, silicon halide is used as a gas for supplying Si to form a lower layer on a desired support. Although the lower layer can be formed, 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. A layer may be formed.

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 silicon compounds containing nitrogen are effectively used as the gas for supplying halogen atoms.

Hydrogen halides such as Hl, S iHs F, S t
H2Fz, 5iHFa, SiH2I2. SiH*C
12゜S 1Hc1s, S iHz Brz,
Substances in a gaseous state or that can be gasified, such as halogen-substituted hydrogen silicides such as S.1HBrs, are also effective lower layers.
It can be mentioned as a raw material for chemical production. 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 lower layer. In the present invention, it is used as a suitable halogen supply gas.

In order to structurally introduce hydrogen atoms into the lower layer, in addition to the above, Hl, 5IH4,5xiHs+Si, H, .
SiH,. 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 the deposition chamber.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) that can be contained in the lower layer, for example, the support temperature and/or the inclusion of hydrogen atoms (H) or halogen atoms (X) can be controlled. 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 (CNOc) that adjust durability into the lower layer, such as carbon atoms (C), nitrogen atoms (N), or oxygen atoms (0), carbon A raw material for introducing atoms (C), a raw material for introducing nitrogen atoms (N), or a raw material for introducing oxygen atoms (0) is placed in a gaseous state in a deposition chamber in order to form a lower layer. It is sufficient to introduce it together with the raw material. 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 room temperature and 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,), prono(n (Cs Ha )+
n-Butane (n Ca Hto) e Pentane (C
,H,,), and the ethylene hydrocarbons include ethylene (
C2H,), propylene (C,H,), butene-1 (C
,H,), butene-2 (C,H,), isobutylene (C
,H,).

Pentene (C,H,.), acetylene (C,H,), methylacetylene CCs as acetylene hydrocarbons
H,), butyne (C4H@), and the like.

As a raw material gas containing Si, C, and H as constituent atoms, S
Mention may be made of alkyl silicides such as i (CHI)41 St (Ct Hs)4.

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 (NH4Ng), nitrogen compounds such as nitrides and azides.

In addition to this, nitrogen trifluoride (F
Examples include halogenated nitrogen compounds such as nitrogen tetrafluoride (F4N) and nitrogen tetrafluoride (F4N). - Starting materials that can be effectively used as raw material gases for introducing oxygen atoms (0) include, for example, oxygen (0,), ozone (0,'), nitrogen dioxide (No), and nitrogen dioxide (N
O, ), -nitrogen dioxide (N, O), nitrogen sesquioxide (N,
O,), trinitrogen tetraoxide (N* 04), nitrogen sesquioxide (
N, O,).

For example, disiloxane (H3S iOS iHs ) + tridioquine (Hs S i O8iH・z O8iH
Examples include lower siloxanes such as s).

In order to structurally introduce atoms (Mc) that adjust image quality into the lower layer, for example, group II atoms, group V atoms, or group VI atoms, group II atoms must be introduced during layer formation. The raw material for the deposition, the raw material for introducing Group V atoms, or the raw material for introducing Group VI atoms may be introduced in a gaseous state into the deposition chamber together with other raw materials for forming the lower layer. Materials that can be used as a raw material for introducing Group I atoms, a raw material for introducing Group V atoms, or a raw material for introducing Group VI atoms are gaseous at room temperature and normal pressure, or at least under layer-forming conditions. It is desirable to use a material that can be easily gasified. Specifically, as raw materials for introducing such Group Ⅰ atoms, B, H, etc. are used for introducing boron atoms.

B4H+o, B-He, Bs H+, B6H+. .

Boron hydride, BF, such as B, H,, B, H,, etc.

Examples include boron halides such as B C13 and B B r s. In addition, A I C1s * G a Cl
sr Ga(CHs)s, InC1a, Tl
Cl5 etc. can also be mentioned.

In the present invention, as a raw material for introducing a group V atom, P Hs is effectively used for introducing a phosphorus atom.
, hydrogen north neighbor such as P x H4, PH41゜PFm,
PFs, PClm, PCli, PBrs.

Examples include halogen north neighbors such as PBrs and Pis. In addition, ASHs, AsF5, AsC15*AsBr5
, AsF5 + 5bHs, 5bFs.

SbF6 + 5bCIs + 5bCIs r BI
Hi + B1C15, B1Br5, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

Hydrogen sulfide (H
, S), SF4. SF,,SQ,,So□F,.

CO8, C8,, CH, SHC, H, SH, C, H, S
.

(CH,), S (C,H,), S, and other gaseous or gasifiable substances may be mentioned. In addition, 5eHz
I SeF6 # (cHs)2 Se, (CIHs
)* Se, TeHz, TeFi e (CHs
)*Te, CCs Ha )* Substances that are in a gaseous state or can be gasified can be mentioned.

In addition, raw materials for introducing atoms (Me) to control the image quality are Hs and He as necessary.

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

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

In addition, in the present invention, the end face of the lower layer with the aluminum-based support is the aluminum atom (AI) of the lower layer.
This is a region in which the content of aluminum atoms (A1) is 95% or less of the content of aluminum atoms (A1) in the aluminum-based support.

This is because in a composition region where the content of aluminum atoms (A1) 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 (AI) in the lower layer exceeds 5%.

This is because in a composition range where the content of aluminum atoms (AI) 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 gas pressure in the deposition chamber is appropriately selected in the optimum range according to the layer design, but normally it is between lXl0-' and 10 Torr.
r, preferably lXl0-'~3T.

rr, optimally lXl0-'~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 5xlO-' to 10W/c. resistance, preferably 5
X10-'~5W/crrr.

Optimally I x 10"" to 2 x 10-'W/
It is preferable to set the value to "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, but it is desirable to determine the optimum value of the lower layer forming factor based on mutual and organic relationships in order to form a lower layer having desired properties.

Top 11 layers The upper layer in the present invention is Non-8t (H.

X) and has desired photoconductive properties.

At least the layer region of the upper layer in contact with the lower layer in the present invention contains atoms (M) that control conductivity, but
Substantially none of carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge), and tin atoms (S n) are contained. However, in other layer regions of the upper layer, atoms (M) controlling conductivity,
It may contain at least one of a carbon atom (C), a nitrogen atom (N), an oxygen atom (0), a germanium atom (Ge), and a tin atom (Sn). 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).

The conductivity controlling atoms (M) contained in the layer region of the upper layer that is in contact with at least the lower layer may be uniformly distributed throughout the layer region, or may be distributed uniformly throughout the layer region. None (Although it is contained, there may be a portion where it is distributed non-uniformly in the layer thickness direction. However, in any case, the in-plane direction parallel to the surface of the support In order to make the properties uniform in the in-plane direction, it is necessary that the content be uniformly distributed.

Atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge
), a tin atom (Sn), an atom (M) that controls the conductivity, a carbon atom (
C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge), and tin atoms (Sn) may be uniformly distributed throughout the layer region, or may be distributed uniformly throughout the layer region. Although it is contained evenly, there may be a portion where it is contained in a non-uniformly distributed state in the layer thickness direction. However, in any case, in the in-plane direction parallel to the surface of the support, it is uniformly distributed and evenly distributed (this is necessary from the point of view of making the properties uniform in the in-plane direction). be.

Also, carbon atom (C) and/or nitrogen atom (N) and/or oxygen atom (0) (hereinafter [atom (CNO) J
(hereinafter referred to as [layer region (CNO)
), abbreviated as J), germanium atom (Ge) and/
Alternatively, a layer region (hereinafter abbreviated as "layer region (GS) J") containing tin atoms (Sn) (hereinafter abbreviated as "atoms (GS) J") contains atoms (M) that control conductivity (hereinafter "atoms (GS) J"). A layer region may be shared in a part of the surface side of at least the layer region in contact with the lower layer (hereinafter abbreviated as "layer region (M, )J") containing atoms (abbreviated as "layer region (M)"). .

In addition, a layer region (hereinafter abbreviated as "layer region (Mr) J") containing atoms (M) other than the layer region (M,), and a layer region (M
, ) and the layer region (M,) are collectively abbreviated as "layer region (M)"), the layer region (CNO), and the layer region (GS),
The layer regions may be substantially the same, at least a part of each layer region may be shared, or each layer region 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. (Hereinafter, the layer region (M), layer region (CNO), and layer region (GS) will be referred to as "layer region (Y)" and atoms (
M), atom (CNO), atom (GS゛)
Atom (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. Area (M), layer area (CNO), layer area (GS)
If they are substantially the same layer area, a single layer area (Y) is included in the upper layer, and if they are not substantially the same layer area, multiple layer areas (Y) are included in the upper layer. (It is mounted).

17 to 36, the horizontal axis shows the distribution concentration C of atoms (Y), the vertical axis shows the layer thickness of the layer region (Y), and t is the end face of the layer region (Y) on the lower layer side. , and 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 formed as a layer from the t side toward the 11 side.

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

In the example shown in FIG. 17, the distribution concentration C of the contained atoms (Y) is the concentration CI? from position t6 to position rl t r. A distribution state is formed in which the concentration increases gradually and continuously from + to a concentration C11 at position 11.

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 the position ts to the position t1111, and increases to the concentration CIII at the position t1.1. Therefore, from position tIl+ to position 11
Up to the concentration C1, a distribution state is formed that takes a constant value.

In the example shown in FIG. 19, the distribution concentration C of the contained atoms (Y) has a constant value of concentration CIII from position tll to position tIII, and from position t,1 to position tIII. The concentration gradually and continuously increases from C1,1 to C1,2 at position t162,
From position t+@s to position t1, a distribution state is formed in which the concentration takes a constant value C1.

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

The concentration becomes a constant value Cjms until the position t,
. Position t, from 1. , the concentration becomes a constant value of C3°, and from position t2° to position t7, the concentration becomes C8.
It forms a distribution state that takes a certain value.

In the example shown in FIG. 21, the distribution concentration C of the contained atoms (Y) forms a distribution state in which the concentration C□ is a constant value from the position tm to the position t7.

In the example shown in FIG. 22, the distribution concentration C of the contained atoms (Y) varies from position tll to position t. Concentration C up to 1!
21, and gradually and continuously decreases from the concentration C22 from position t221 to position t↑, and then reaches the concentration C! at position t7. 23 is formed.

In the example shown in FIG. 23, the distribution concentration C of the contained atoms (Y) is the concentration CI 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 at position 1. More position t! Concentration C up to 41
Take a constant value of 341 and move from position t2a□ to position 1T.
It gradually and continuously decreases from the concentration C24 until it reaches .
A distribution such that the distribution concentration C is substantially zero at position tA (substantially zero here means the case where the amount is less than the detection limit, and the meaning of "substantially zero" hereinafter is also the same). forming a state.

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

In the example shown in FIG. 26, the distribution concentration C of the contained atoms (Y) is from position t to position t, up to 6°, the concentration ca
A distribution state is formed such that the concentration takes a constant value st, decreases in a linear function from the concentration C28+ from the position t2.1 to the position 11, and reaches the concentration C36 at the position tT.

In the example shown in FIG. 27, the distribution concentration C of the contained atoms (Y) is the concentration C! from position t to position t7.
A distribution state is formed in which the distribution concentration C decreases linearly from fI and becomes substantially zero at the position t7.

In the example shown in FIG. 28, the distribution concentration C of the contained atoms (Y) is from position t to position t2. .

Until then, the concentration takes a constant value Cmar, and from position t, □, position t? Concentration up to C! , 1, and decreases linearly from 1 to form a distribution state such that the concentration C2, , is reached at position t7.

In the example shown in FIG. 29, the distribution concentration C of the contained atoms (Y) is from position t to position 11 at a concentration C8.
, , gradually and continuously decreases, forming a distribution state in which the concentration C11 is reached at position 11.

In the example shown in FIG. 30, the distribution concentration C of the contained atoms (Y) takes a constant value of concentration C1°1 from position t to position t1.1, and from position t. From 1 to position t7, the concentration is C. , and decreases in terms of the number of degrees, forming a distribution state such that the concentration becomes C1° at position t7.

In the example shown in FIG. 31, the distribution concentration C of the contained atoms (Y) is from position t to position t□1.
□, gradually and continuously increases from position t11. A distribution state is formed in which the concentration is C112 at the position t□1 and the concentration C31m is a constant value from the position t□1 to the position tT.

In the example shown in FIG. 32, the distribution concentration C of the contained atoms (Y) is the concentration C from position tll to position 11.
Concentration C1! increases gradually and continuously from 1l until the concentration C1! ! The distribution state is formed as follows.

In the example shown in FIG. 33, the distribution concentration C of the contained atoms (Y) is from position t to position t3. .

The value gradually increases from substantially zero (substantially zero here refers to the case where the amount is less than the detection limit; the meaning of "substantially zero" hereinafter also applies) until it reaches position t1. ．． The concentration becomes C1l at position t8. .

A distribution state is formed in which the concentration takes a constant value c ssi up to position t7.

In the example shown in FIG. 34, the distribution concentration C of the contained atoms (Y) gradually increases from substantially zero from position tll to position t7, and at position t7 the concentration C84,
The distribution state is formed as follows.

In the example shown in FIG. 35, the distribution concentration C of the contained atoms (Y) increases linearly from the concentration CIII from the position t to the position tIII, and then increases from the concentration CIII to the position t181.
A distribution state is formed in which the concentration Cssi 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 C361 up to the position t7.
The concentration C3 increases at position 11 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 atoms belonging to Group ■ of the periodic table, excluding oxygen atoms (0) (hereinafter abbreviated as "Group V atoms")
Hereinafter abbreviated as "Group I atoms") will be used. Specific examples of the Group II atoms include B (boron), AI (aluminum), Ga (gallium), In (indium), and TI (thallium), with B, AI, and Ga being particularly preferred.

Specific examples of Group V atoms include P (phosphorus), As (arsenic), sb (antimony), and Bi (bismuth), with P and As being particularly preferred. Specific examples of 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). Controlling effects and/or
or the effect of selectively controlling or improving the charge injection property or charge injection blocking property between the layer region (M) and the lower layer and/or the layer region of the layer region (M) and the upper layer; It is possible to obtain the effect of improving the charge injection property between layer regions other than (M). The content of atoms (M) that control conductivity contained in the layer region (M) is preferably l
Xl0-'' to 5X104 atomic ppm, more preferably 1
×10-1 ~ I X 104 atoms 1) 9m% Optimally l
It is desirable that the amount is from Xl0-' to 5X10'' atomic ppm.

In particular, in the layer region (M), carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0
) is less than 1 x 10” atomic ppm,
Atoms (M) that control conductivity contained in the layer region (M)
) content is preferably 1xlO-” to 1xl
It is preferable that the carbon atom (C)
and/or nitrogen atom (N) and/or oxygen atom (
If the content of 0) exceeds 1 x 10s atomic ppm,
The content of atoms (M) that control conductivity is desirably 1X10-1 to 5X10' 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' atoms ppm5 more preferably lXl0' to 5X1
0' atomic ppm, optimally 1xlO'' to 3xlO' atomic ppm. Particularly when aiming at high dark resistance and/or high hardness, preferably lXl0''
It is desirable to set it to ~9X10' atomic ppm, and when controlling the spectral sensitivity, preferably 1x102 to 5X1
It is desirable that the content be 0' atomic ppm.

In the present invention, by containing germanium atoms (Ge) and/or tin atoms (Sn) in the layer region (GS), it is possible to mainly control the spectral sensitivity, particularly when using a semiconductor laser or the like as an image exposure source of an electrophotographic device. The effect of improving long wavelength light sensitivity when using long wavelength light can be obtained. Germanium atoms (
The content of Ge) and/or tin atoms (S n) is preferably 1 to 9.5X10' atoms 1) 9m%, more preferably 1x102 to 8X10' atoms ppm%, and optimally 5X10'' to 7X10' atoms. It is desirable to set it as 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 sum of the content of I) and the halogen atom (X) is preferably 1X10'' to 7X10' atoms ppm, and the content of the halogen atom (X) is preferably 1 to 4X
Preferably, the amount is 10' atoms ppm.

In particular, the above-mentioned carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) in the upper layer
If the content of
) is 1X10''~4X10' atomic ppm
It is desirable that this is done. Furthermore, when the upper layer is composed of a polycrystalline material, hydrogen atoms (H), or hydrogen atoms (H) and halogen atoms (X) contained in the upper layer
The sum of the contents is preferably I x 10'' to 2 x 10'
It is desirable that the number of atoms is 9 x 10', and in the case of a non-crystalline structure, it is preferably 1 x 104 to 7 x 10' atoms.
It is desirable to set it as pm.

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

For example, Non-8i (H
, X), basically a Si supply gas capable of supplying silicon atoms (St);
N supply gas that can supply hydrogen atoms (H) and/or X supply gas that can supply halogen atoms (X), and M that can supply atoms (M) that control conductivity as necessary
Supply gas and/or C supply gas capable of supplying carbon atoms (C) and/or N supply gas capable of supplying nitrogen atoms (N) and/or C supply gas capable of supplying oxygen atoms (0) gas and/or germanium atoms (G
A Ge supplying gas capable of supplying e) and/or a Sn supplying gas capable of supplying tin atoms (Sn) are introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure. A glow discharge may be generated to form a layer made of Non-8i (H,

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

To form the upper layer composed of Non-8i (H,
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 C supply gas capable of supplying oxygen atoms (0); and/or Ge supply gas capable of supplying germanium atoms (Ge); and/or A Sn supplying gas capable of supplying tin atoms (Sn) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, separately or together as required, and further halogen (Sn) is introduced into the deposition chamber at a desired gas pressure. X) 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 installed in a predetermined position in advance. Non-8i (H,
) may be formed.

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

In the present invention, when forming the upper layer, atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), germanium atoms (Ge) that control conductivity are contained in the upper layer.
, tin atom (Sn) (hereinafter these will be collectively referred to as "atom (M
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 profi-1e), the raw material gas for supplying atoms (MCNOGS) whose distribution concentration should be changed is adjusted to the desired gas flow rate. This is accomplished by changing the amount appropriately according to a rate of change curve and introducing it into the deposition chamber.

For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system is 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 5iHa, 5iffiHa131@H
ll, S 1 a H+. Silicon hydride (silanes) in a gaseous state or that can be gasified are mentioned as those that can be effectively used, and 5iHn and 5ixHs are also effective in terms of ease of handling during layer creation work and good Si supply efficiency. are listed as preferred. In addition, these raw material gases for supplying Si may be converted into H, He, Ar, Ne, etc. as necessary.
It may be used after being diluted with gas such as.

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

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

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CIF, ClF5. BrF5. BrF
,,IFs,IFy.

Interhalogen compounds such as ICI and IBr can be mentioned.

Examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include SiF4. Preferred examples include silicon halides such as Six Fs, 5iC14, 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. Non-8i (H,X) containing halogen atoms on the desired support
A top layer consisting of - can be formed.

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 halogenated gases such as HF, HC1°HBr, and HI are also effective. Hydrogen, S iHs F +5iHz F2.5iHFs, S
tH*i,, 5iHz C1z, 5iHC1s, 5
iHs Brz.

Gaseous or gasifiable substances such as halogen-substituted silicon hydrides such as 5iHBrs 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.

In order to structurally introduce hydrogen atoms into the upper layer, in addition to the above, B2, SiH4, Six H8゜3il
This can also be carried out by causing a discharge by causing silicon hydride such as H@, S 1 a Hlo, etc., and silicon or a silicon compound for supplying Si to coexist in the 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 a raw material for introducing group (III) atoms, a raw material for introducing group V atoms, or a raw material for introducing group (■) atoms may be gaseous at room temperature and pressure, or at least under layer forming conditions. It is desirable to use a material that can be easily gasified by oxidation. Specifically, as raw materials for introducing such Group Ⅰ atoms, B, H, etc. are used for introducing boron atoms.

B.H. , B, B9. B6HIl, B6H1゜, B.

H+ j* B a Boron hydride such as Hla, BF,
Be1l.

Examples include boron halides such as BBr. In addition,
AlC1, GaC15, Ga(CHs)s.

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 P, H, etc., PH4I.

PFs + PFs, PCIn, 'PC1i, P
Brs.

Examples include halogen north neighbors such as PBr and PIs. In addition, AsH, AsF5, AsC15.

AsBr5, AsF5.5bHs, 5bFi +5
bFs+ 5bc1s, 5bC1s, B11(s.

B1C1m, B1Br5, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

Hydrogen sulfide (H,
S) , SF, , SF, , SQ, , So, F,
.

CO8, C8,, CHI SH, C, H, SH.

Substances that are in a gaseous state or can be gasified, such as C, H, S, (CH,), S, (C, H,), S, etc., may be mentioned. In addition, S eHs, S e F@, (C)1m)*S
e, (Ct Hs )s Se, TeHs + TeF
Examples include substances in a gaseous state or which can be gasified, such as a + (CHs )z Te, (C2H6)2 Te, and the like.

Further, the raw material for introducing atoms (M) for controlling conductivity may be diluted with a gas such as Ha, He, Ar+Ne, etc., as necessary.

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 a raw material for introduction or a raw material for introducing oxygen atoms (0), it is preferable to use a material that is gaseous at room temperature and normal pressure, or at least can be easily gasified under layer-forming conditions. 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 (C,H,), propane (C.

Hs) on-butane (n C4Hto) + pentane (C, H, 2), ethylene hydrocarbons include ethylene (C, H,), propylene (C, H,).

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

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

Acetylene (C.

H3), methylacetylene (cs H,>, butyne (
C, H, ), etc.

As a raw material gas containing Si, C, and H as constituent atoms, S
i (CHI) a, S i (Cx Ha
) s, etc. can be mentioned.

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 (NHI), hydrazine (H, NNH,)
, hydrogen azide (HNs).

Mention may be made of gaseous or gasifiable nitrogen such as ammonium azide (NH4Ns), nitrogen compounds such as nitrides and azides. In addition, nitrogen atoms (N)
In addition to the introduction of halogen atoms (X), nitrogen trifluoride (F$N) and nitrogen tetrafluoride (F$N) can also be introduced.
Examples include halogenated nitrogen compounds such as 4N, ).

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

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

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

04), nitrogen sesquioxide (N*Os>, nitrogen trioxide (
For example, disiloxane (No, ), silicon atom (Si), oxygen atom (0), hydrogen atom (H) and constituent atoms
Hs 5iO8iHs) + ) Rishiokin (Hs
Examples include lower siloxanes such as S i O8i Hz O8i Ha ).

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

As a substance that can be used as a raw material gas for supplying Ge, G e
Ha + G ea Ha + G es Ha r
G eaHIIl+ Ges H1*I Ges O1
4, Get H1@IG ea Hta, Ges H
Germanium hydride in a gaseous state such as 2° or which can be gasified can be effectively used, and in particular, GeH4, Get Hs , Ges Ha are preferred.

In addition, GeHF5, GeHz Fx, GeHsF
, GeHCl5, GeH2C12, GeH
sCI, GeHBr5, GeHtBr
z, GeHsBr, GeHls, GeHB
r5, hydrogenated germanium halide such as GeHs I, GeF4゜GeC14* GeBrn, Ge
14, GeFz *G e Cl 2 , G e
Examples include germanium halides such as B r 2 and G e I z .

Substances that can be used as raw material gas for supplying Sn include Sn
Ha + S n z Ha * S n * Ha
* Sn aHlo+ Sns H+z+ Sn
a H141Snt H1@l5n8 H+a, Sno
) LOI and other gaseous or gasifiable tin hydride can be effectively used, especially in terms of ease of handling during layer formation work, good Sn supply efficiency, etc. Ha, Sns H
s + is preferred.

In addition, 5nHFs, SnH*F! ,5nHsF
, 5nHCj! s, 5nHz C1*, 5nHsC
I! , 5nHBrs , 5nHi Brz , SnHm
Br, 5nl-11s, 5nHa I2, 5n
Hydrogenated tin halide such as Hs I, 5nFa, 5nC
z4+5nBrn, SnI4, SnF*, 5n
C1*.

5nBrz, Sn1. Gaseous or gasifiable substances such as tin halides and the like 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 gas pressure in the deposition chamber is selected according to the layer design, but normally it is lXl0-'~10 Torrs.
Preferably I x 10-' to 3 Torr.

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

The upper layer is Non-8i (H,X) and hydrogen atoms (H
) and/or A-3 containing a halogen atom (X)
i (hereinafter abbreviated as rA-8i (H, , 50-400°C, suitable: The temperature of rice is preferably 100-300°C.

The upper layer is Non-8i (H,X) and hydrogen atoms (H
) and/or halogen atoms (X) (hereinafter abbreviated as rpoly-8i(H,X)J), there are various methods for forming the layer. There are several methods, such as the following.

One method is to increase the support temperature to a high temperature, specifically 40°C.
In this method, the temperature is set at 0 to 600° C., and a film is deposited on the support by plasma CVD.

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

In the present invention, when the upper layer made of Non-8i (H, 5X10-@~IOW/cm
'', preferably 5×10-' to 5 W/cm, optimally 1X10-'' to 2×10-'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 upper layer include the above-mentioned ranges, but these layer creation factors are usually It is preferable to determine the optimum value of the upper layer forming factor based on mutual and organic relationships, rather than being determined separately and independently.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but 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.

- Figure 37 shows the raw material gas supply device 1020 and the deposition device 1.
000, which is an apparatus for manufacturing an electrophotographic light-receiving member using an RF glow discharge decomposition method.

1071.1072, 1073.1074.10 in the diagram
75,1076.1077 gas cylinder and 1078
The raw material gas for forming each layer of the present invention is sealed in the sealed container, and 1071 is SiH4 gas (
1072 is a H, gas (purity 99.9999%) cylinder, 1073 is a CH4 gas (purity 99°999%) cylinder, 1074 is a PH gas diluted with H, gas (purity 99 .999%, hereinafter referred to as rPH,
/H, J) cylinder, 1075 is B i H gas diluted with H2 gas (purity 99.999%, hereinafter abbreviated as rB, Ha /H2J), 1076 is No gas (purity 99.9 %) cylinder, 1077 is a He gas (purity 99.999%) cylinder, and 1078 is a sealed container filled with AICIm (purity 99.99%).

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

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

Next, the vacuum gauge 1017 reads approximately 1X10-”T.

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

After that, S i H4 gas from gas cylinder 1071, H gas from gas cylinder 1072, CH4 gas from gas cylinder 1073, PH, /H gas from gas cylinder 1074, B*Hs/Ht gas from gas cylinder 1075, No gas from gas cylinder 1076, gas cylinder 10
77, He gas was introduced by opening valves 1051 to 1057, and the pressure of each gas was adjusted to 2 K g/cm'' by pressure regulators 1061 to 1067.

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.
Since it passes through a closed container 1078 filled with lC1, AlC1 gas (hereinafter rA1c) diluted with He gas
1. /HeJ) is introduced.

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

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

To form the bottom layer, the outflow valves 1041°1042
．． 1044.1047 and the auxiliary valve 1018 are gradually opened to supply S i H4 gas, H, gas, S i F a
The 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, the SiH4 gas flow rate is 508 CCM, the H gas flow rate is 1108 CC, and the AlC1, /He gas flow rate is 1.
Each mass flow controller 1021, 1022, 1024, 1027 was adjusted to 208 CCM. 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 0.4 Torr. After that, the power of the RF power supply (not shown) is
mW/cm” and high frequency matching box 101.
2, RF power is introduced into the deposition chamber 1001 through RF
A glow discharge was generated to initiate the formation of a lower layer on the cylindrical aluminum-based support. During the formation of the bottom layer, SiH4
The SiF gas flow rate was adjusted to a constant flow rate of 508 CCM.
4 gas flow rate is H so that it becomes a constant amount of 58CCM, and AlC1,/He gas flow rate is 120S so that the gas flow rate increases at a constant rate from IO8CCM to 200SCCM.
Mass flow controller 1021.1022°102 to decrease at a constant rate from CCM to 40SCCM
4.1027 was adjusted to form a lower layer with a layer thickness of 0.05 μm, the RF glow discharge was stopped, and the outflow valves 1041, 1042, 1044, 1047 and the auxiliary valve 1018 were closed to allow the flow into the deposition chamber 1001. The gas flow was stopped, and the formation of the lower layer was completed.

Next, to form the first layer area of the upper layer, the outflow valves 10, 41, 1042, 1045 and the auxiliary valve 1
Gradually open 018 and add SiH4 gas, H, gas, B, H
, /H, gas is supplied to the gas discharge hole 100 of the gas introduction pipe 1008
9 into the deposition chamber 1001. At this time, S
I Ha gas flow rate is 1001005CC, gas flow rate is 500SCCMSB, H, /H2 gas flow rate is S I H
Each mass flow controller 1021, 1022, and 1025 was used to adjust the amount to 200 ppm with respect to a. While checking the vacuum gauge 1017, adjust the pressure in the deposition chamber 1001 to 0.4 Torr by turning the main valve 1016.
Adjusted the aperture. Thereafter, the power of an RF power source (not shown) is set to 8 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 upper layer is formed on the lower layer. After forming the first layer region of the upper layer with a layer thickness of 3 μm, the RF glow discharge is stopped, and the outflow valve 1041, 1042, 1045 and the auxiliary valve 1018 are closed, and the deposition The flow of gas into the chamber 1001 was stopped, and the formation of the first layer region of the upper layer was completed.

Next, to form the second layer region of the upper layer, the outflow valves 1041, 1042 and the auxiliary valve 1018 are gradually opened to supply SiH4 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 was 3008CCM,
The mass flow controllers 1021 and 1022 were used to adjust the H gas flow rate to 3008 CCM.

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 increased to 15
mW/cm” and high frequency matching box 101.
2, RF power is introduced into the deposition chamber 1001 through RF
A glow discharge is generated, the formation of a second layer region is started on the first layer region of the upper layer, and when the second layer region of the upper layer with a layer thickness of 20 μm is formed, the RF glow discharge is stopped, and , outflow valve 1041.1042 and auxiliary valve 1
018 was closed to stop the flow of gas into the deposition chamber 1001, and the formation of the second layer region of the upper layer was completed.

Next, to form the third layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened to supply SiHa gas, CH, and gas to the gas inlet pipe 10.
08 into the deposition chamber 1001 through the gas discharge hole 1009. At this time, the SiH4 gas flow rate is 508CCM
, CH, and gas flow rates were adjusted to 5008 CCM using mass flow controllers 1021 and 1023, 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 0.4 Torr. After that, the power of the RF power supply (not shown) is
RF power is introduced into the deposition chamber 1001 through a high frequency matching box 1012 set at 0 mW/c g to create an RF glow discharge and form a third layer region on the second layer region of the upper layer. The RF glow discharge is stopped after forming the third layer region of the upper layer with a layer thickness of 0.5 μm, and the outflow valves 1041, 1043 and the auxiliary valve 1018 are closed to allow the gas to enter the deposition chamber 1001. The inflow was stopped and the formation of the third 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 enters the deposition chamber 1001 and the outflow valve 104.
In order to avoid remaining in the piping from 1 to 1047 to the deposition chamber 1001, the outflow valves 1041 to 1047
, close the auxiliary valve 1018, and then fully open the main valve to temporarily evacuate the system to a high vacuum, as necessary.

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

<Comparative Example> An electrophotographic light-receiving member was produced under the same production conditions as in Example 1, except that H and 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.

It was found that both of these light-receiving members for electrophotography have the characteristic of exhibiting extremely good charging ability, but when comparing the number of holes as an image characteristic, it was found that
It was found that the electrophotographic light-receiving member of Example 1 had a number of spots less than half that of the electrophotographic light-receiving member of Comparative Example with respect to the number of spots of m or less. Furthermore, in order to compare the degree of roughness, image density was measured at 100 points with a circular area with a diameter of 0.05 mm as one unit, and the variation in image density was evaluated. The variation in the receiving member is less than 1/2 that of the electrophotographic light receiving member of the comparative example, and visually the electrophotographic light receiving member of Example 1 is superior to the electrophotographic light receiving member of the comparative example. I understand.

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

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

(Example 2) By further using No gas, BtHa/H, and gas in the lower layer of Example 1, and changing the way the A I C1s/He gas flow rate was changed, and under the production conditions shown in Table 3, Example 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 spots, roughness, and layer peeling.

<Example 3> In the upper layer of Example 1, CH and gas were not used, and the fourth
A light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in the table, and the same evaluation was conducted. The effect was obtained.

<Example 4> In Example 1, N, gas (purity 99.9999%),
Further using He gas (purity 99.9999%), an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 5, and the same evaluation was performed. Similarly, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 5> In Example 1, instead of AlC1, AI(CHs)s
(longitude 99.99%), and in the upper layer S i
F' gas cylinder with Ar gas (purity 99.9999%)
Change the No gas cylinder to NH, gas (purity 99
．． 999%) instead of the cylinder, an electrophotographic light-receiving member was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 6, and the same evaluation was performed.
A good effect of improving roughness and layer peeling was obtained.

<Example 6> PH, /HaHe gas etc. are 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 conducted. The effect was obtained.

<Example 7> PHF diluted with He gas in the lower layer of Example 1
, i gas (purity 99.999%, hereinafter r P F s
/ He J) and B in the upper layer.
2 H6/Hm, further using S i F4 gas,
An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 8, and the same evaluation was conducted.
As in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 8> H and S gases were used in the lower layer of Example 1, and PH and /H2 gases and N and gas were further used in the upper layer,
An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 9, and the same evaluation was conducted.
As in Example 1, good effects were obtained to improve the appearance of edges, roughness, and layer peeling.

<Example 9> In Example 1, CH and gas cylinders were C and H.

A light-receiving member for electrophotography was produced in the same manner as in Example 1 using a gas (purity 99.9999%) cylinder under the production conditions shown in Table 10, and the same evaluation was performed. A good effect was obtained to improve the appearance of spots, roughness, and layer peeling.

(Example 10) In the lower layer of Example 1, BF diluted with He gas
, gas (purity 99.999%, hereinafter abbreviated as "BF, /HeJ") and according to the preparation conditions shown in Table 11,
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 edges, roughness, and layer peeling.

<Example 11> In the same manner as in Example 1, the No gas cylinder was changed to an NH, gas cylinder, and the CHa gas in the upper layer was changed to NH, gas. A receiving member was prepared and evaluated in the same manner as in Example 1, and as in Example 1, good effects were obtained in improving dents, 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 the effects of creases, roughness, and layer peeling.

<Example 13> In the lower layer, 5iiHs gas (purity 99°99%) was used instead of S I Fa gas, and in the upper layer, B
Hiroshi H*/H-gas, Si*Ha gas (purity 99.9
9%) was used to prepare an electrophotographic light-receiving member in the same manner as in Example 1 under the preparation conditions shown in Table 14, and the same evaluation was performed. , a good effect on layer peeling was obtained.

(Example 14) A light-receiving member for electrophotography was produced in the same manner as in Example 1, using Si*Hs gas in the lower layer and using PH, /H, gas in the upper layer, and under the production conditions shown in Table 15. was prepared and subjected to similar evaluations, and as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 15> In Example 1, the No gas cylinder was replaced with G e H4 gas (
A light-receiving member for electrophotography was prepared in the same manner as in Example 1, using G e H4 gas in the upper layer instead of the cylinder (purity 99.999%), and according to the preparation conditions shown in Table 16. As a result of the evaluation, as in Example 1, good effects were obtained in improving the effects of creases, roughness, and layer peeling.

<Example 16> In Example 1, the outer diameter of the cylindrical aluminum support was set to 80 mm, and an electrophotographic light-receiving member was prepared in the same manner as in Example 1 according to the preparation conditions shown in Table 17. Evaluations were conducted in the same manner as in Example 1, except that an electrophotographic device modified from a copying machine NP-9030 was used for the experiment, and as in Example 1, 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 an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 18. Evaluations were conducted in the same manner as in Example 1, except that an electrophotographic device modified from a copying machine NP-1502 was used for the experiment, and as in Example 1, there were improvements in marks, roughness, and layer peeling. 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 a light-receiving member for electrophotography was prepared in the same manner as in Example 1 according to the preparation conditions shown in Table 20. Evaluations were 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 = o, s
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.
Similar to the above, good effects were obtained in improving burrs, roughness, and layer peeling.

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

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

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゜1044.1045,1046.1
047 and the auxiliary valve 1018 gradually open.
, H, gas, and A I C1s/He gases were 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
Ha gas flow rate is 1508CCM, H gas flow rate is 20S
CCM, SiF, gas flow rate is 1108CC, No gas flow rate is IO8CCM, B.

H, /H, gas flow rate is 50 ppm relative to SiH4 gas
Each mass flow controller 1021.
Adjusted at 1022, 1024, 1025° 1026.1027. The pressure inside the deposition chamber 1101 is 0.6 mTor.
While checking a vacuum gauge (not shown), the opening of the main valve (not shown) was adjusted so that the temperature was r. After that, the power of a μW power source (not shown) is set to 0.5 W/pm'', and the plasma generation region 1109 is
μW power was introduced into the cylindrical aluminum support 1107 to generate a μW glow discharge, thereby starting the formation of a lower layer on the cylindrical aluminum-based support 1107. During the formation of the bottom layer, the SiH4 gas flow rate was 150
SCCM, SiF4 gas flow rate is IO3C0MSNo gas flow rate is 10SCCM, B, H, /H, gas flow rate is 5tH
The H2 gas flow rate was increased at a constant rate from 20SCCM to 500SCCM, and the AlC1,/He gas flow rate was increased at a constant rate from 400SCCM to 80SCCM at 0.01 μm on the support side. The mass flow controller 1021.1022°1 is adjusted so that the mass flow rate decreases at a constant rate from 80SCCM to 50SCCM at 0.01 μm on the upper layer side.
024.1025, 1026.1027, and when a lower layer with a layer thickness of 0.02 μm was formed, the μW glow discharge was stopped, and the outflow valves 1041.1042, 104
4,1045,1046°1047 and auxiliary valve 1
018 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, B, H,
/Hz gas was flowed into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, the SiH4 gas flow rate is 1003 CCMSH, the gas flow rate is 500 SCCM, B, H, /H, and the gas flow rate is S
Each mass flow controller 1021゜1022.10 so that the iHa gas flow rate is 200 ppm.
Adjusted to 25. The pressure inside the deposition chamber 1101 is 0.5 m
It was adjusted so that Torr. After that, μW (not shown)
Reduce the power of the power supply to 0. 5 W/cm", a μW glow discharge is generated in the plasma generation chamber 1109 in the same manner as the lower layer, and the formation of the first layer region of the upper layer is started on the lower layer, and the upper layer with a layer thickness of 3 μm is formed. A first layer region was formed.

Then to form the second layer region of the upper layer, the outflow valves 1041, 1042, 1044 and the auxiliary valve 101
8 gradually open S iH4 gas, H, gas, S i
F 4 gas was allowed to flow into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110 . At this time, S I H4 gas flow rate is 7008CCM, H gas flow rate is 500SCCM, SiF, gas flow rate is 308CC
Each mass flow controller 102
Adjusted with 1.1022.1024. The pressure inside the deposition chamber 1101 was set 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 region 1109, and an upper layer with a layer thickness of 20 μm is formed on the first layer region of the upper layer. A second layer region was formed.

Next, to form the third layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened to supply SiH4 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 S i Ha gas flow rate is 1
508CCM.

Each mass flow controller 1021 and 1023 was adjusted so that the CH4 gas flow rate was 5008 CCM.

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/cr.
rr, a μW glow discharge is generated in the plasma generation region 1109, and a layer thickness of 1μ is formed on the second layer region of the upper layer.
A third layer region of the upper layer of m was formed.

Table 1 22 shows the conditions for producing the above light-receiving member for electrophotography.

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 edges, roughness, and layer peeling.

<Example 24> An electrophotographic light-receiving member was produced in the same manner as in Example 29 under the production conditions shown in Table 23, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 25) An electrophotographic light-receiving member was produced in the same manner as in Example 10 under the production conditions shown in Table 24, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 26> An electrophotographic light-receiving member was produced in the same manner as in Example 11 under the production conditions shown in Table 25, and the same evaluation was performed. A good effect was obtained, which improved the results.

<Example 27> An electrophotographic light-receiving member was produced in the same manner as in Example 12 under the production conditions shown in Table 26, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 28> An electrophotographic light-receiving member was produced in the same manner as in Example 13 under the production conditions shown in Table 27, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 29> An electrophotographic light-receiving member was produced in the same manner as in Example 14 under the production conditions shown in Table 28, and the same evaluation was performed. A good effect was obtained that improved the results.

(Example 30) An electrophotographic light-receiving member was produced in the same manner as in Example 4 under the production conditions shown in Table 29, and the same evaluation was performed. A good effect was obtained that improved the results.

(Example 31) An electrophotographic light-receiving member was produced in the same manner as in Example 6 under the production conditions shown in Table 30, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 32> An electrophotographic light-receiving member was produced in the same manner as in Example 12 under the production conditions shown in Table 31, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 33> An electrophotographic light-receiving member was produced in the same manner as in Example 31 under the production conditions shown in Table 32, and the same evaluation was performed. A good effect was obtained that improved the results.

Table 1 Table 2 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8 Table 9 Table 10 Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 17 Table 18 Table 19 Table 20 Table 21 Table 22 Table 23 Table 24 Table 25 Table 26 Table 27 Table 28 Table 29 Table 30 Table 31 Table 32 [Effects of the invention] ] By making the electrophotographic light-receiving member of the present invention have the specific layer structure as described above, all the problems in the conventional electrophotographic light-receiving member composed of A-8t can be solved, and in particular, Extremely excellent electrical and 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. The ability to inject charges (photocarriers) between the layers is improved, and the structural continuity of the constituent elements between the aluminum-based support and the upper layer is improved, so roughness and burrs are eliminated. Image characteristics are improved, halftones appear clearly, and high-quality images with high resolution can be stably and repeatedly obtained.

Furthermore, image defects and non-contamination may occur due to relatively short-term impact mechanical pressure applied to electrophotographic light-receiving members.
It prevents the occurrence of peeling of the 5i (H,
It can alleviate the stress caused by the difference in the thermal expansion coefficient of the (H, .

In particular, in the present invention, halogen atoms (X) in the lower layer
By coexisting with silicon atoms (Si), aluminum atoms (AI), etc., it is possible to compensate for the dangling bonds and obtain a more structurally and structurally stable state. Coupled with the effects of the distribution of hydrogen atoms (Si) and hydrogen atoms (H), it is characterized by a remarkable improvement in image characteristics such as roughness and spots.

Furthermore, in the present invention, by containing atoms (M) that control conductivity in the layer region of the upper layer that is in contact with the lower layer, it is possible to improve the charge injection property or the charge injection blocking property between the upper layer and the lower layer. It is possible to selectively control or improve image characteristics such as roughness and spots, and it is possible to stably and repeatedly obtain high-quality images with clear halftones and high resolution. , charging ability, sensitivity and durability are also improved.

[Brief explanation of the drawing]

FIG. 1 is a schematic block diagram for explaining the layer structure of a light-receiving member for electrophotography according to the present invention. FIG. 2 is a schematic block diagram for explaining the layer structure of a conventional light-receiving member for electrophotography. , FIGS. 3 to 8 respectively show aluminum atoms (AI), halogen atoms (X), atoms that adjust durability (CNOC) and atoms that adjust image quality (CNOC) contained in the lower layer, respectively. Figures 9 to 16 are explanatory diagrams of the distribution state of Mc), respectively, for silicon atoms (Si), hydrogen atoms (H), and halogen atoms (
X), an atom (C
Explanatory diagrams of the distribution states of atoms (M c ) that adjust NOc) and image quality, and FIGS. 17 to 36 are the atoms (M) and carbon atoms (C) that control conductivity contained in the upper layer, respectively. and/or an explanatory diagram of the distribution state of nitrogen atoms (N) and/or oxygen atoms (0), germanium atoms (Ge) and/or tin atoms (Sn), FIG. 37 is an electrophotographic light-receiving member of the present invention A schematic explanatory diagram of a manufacturing apparatus using a glow discharge method using RF, which is an example of an apparatus for forming a light-receiving layer of the present invention, and FIG. FIG. 39 is an enlarged view of the cross section of the support when the cross-sectional shape of the body is V-shaped, and FIG. FIG. 40 is a schematic explanatory diagram of a deposition apparatus when a microwave glow discharge method is used to form the light-receiving layer of the electrophotographic light-receiving member of the present invention; FIG. The figure is an example of an apparatus for forming the light-receiving layer of the electrophotographic light-receiving member of the present invention, and is a schematic explanatory view of a manufacturing apparatus using a glow discharge method using microwaves. 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-3i...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...
Raw material gas cylinder valves 1061 to 106. , ? ...Pressure regulator 1071~
1077... Raw material gas cylinder 1078... Sealed container for raw material In FIGS. 40 and 41, 1100... Deposition device using microwave glow discharge method 1101... Deposition chamber 1102... Dielectric window 1103.・Waveguide part 1107 ・Cylindrical aluminum support 1109 ・
...Plasma generation region 1010...Gas introduction pipe No. 15 [fl No. 17 Old/6 [0 No. 78 El No. ? 31fl No. 25 Old Way 240 No. 26 No. 3/7 No. 33 No. 320 No. 34 Day 38 Must No. 3cI Ward

Claims (1)

Scope of Claims: (1) A light-receiving member having an aluminum-based support and a multi-layer photoreceptive layer exhibiting photoconductivity on the support, wherein the light-receiving layer is arranged as a constituent element from the support side. as at least aluminum atoms, silicon atoms, hydrogen atoms,
a lower layer made of an inorganic material containing halogen atoms and having a portion containing the aluminum atoms, silicon atoms, and hydrogen atoms in a non-uniform distribution state 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 the following, and containing atoms for controlling conductivity in a layer region in contact with the lower layer. (2) The atoms that control conductivity are found in I of the periodic table.
The light-receiving member according to claim 1, which is an atom belonging to Group II. (3) The light-receiving member according to claim 1, wherein the atom that controls conductivity is an atom belonging to Group V of the periodic table, excluding nitrogen atoms. (4) The light-receiving member according to claim 1, wherein the atom that controls conductivity is an atom belonging to Group VI of the periodic table, excluding oxygen atoms.