JPS63276062A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To improve overall characteristics by consisting a photoreceptive layer 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 least either of a germanium atom and tin atom in the region in contact with the lower layer. CONSTITUTION:This photoreceptive member 100 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 at least either of the germanium atom (Ge) and tin atom (Sn) 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. The excellent electrical characteristics, optical characteristics, 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 light-receiving member that is sensitive to light.

[Prior art]

In the image forming field, photoconductive materials constituting the light-receiving layer of light-receiving members are highly sensitive, have a high signal-to-noise ratio (photocurrent (Ip)/dark current (Id)), and are suitable for the spectrum of electromagnetic waves to be irradiated. It has absorption spectrum characteristics that match the characteristics, has fast photoresponsiveness, and has a 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-3i) is a photoconductive material that has recently attracted attention.
Application as a light-receiving member for electrophotography is described in JP 855718 and the like.

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

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

[Problem that the invention seeks to solve]

However, the electrophotographic light-receiving member having the light-receiving layer composed of conventional A-8i has poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, and the usage environment. Although individual improvements have been made in terms of properties, stability over time, and durability,
The reality is that there is room for further improvement in terms of improving overall characteristics.

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

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

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

Furthermore, due to the stress generated due to the difference in thermal expansion coefficient between the aluminum support and the A-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-3t 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 comprises an aluminum-based support and an electron-receiving layer having a multilayer structure having at least photoconductivity on the support. In the photographic light-receiving member, the light-receiving layer is made of an inorganic material (from the support side) containing at least aluminum atoms (AI), silicon atoms (Si), hydrogen atoms (■), and halogen atoms (X) as constituent elements. From now on rA
A lower layer comprising a portion containing aluminum atoms (A1), silicon atoms (Si), and hydrogen atoms (11) in a non-uniform distribution state in the layer thickness direction. and a non-single-crystal material (Si) containing at least one of a hydrogen atom (11) and a halogen atom (X)
an upper layer comprising at least one of germanium atoms (Ge) and tin atoms (S n) in a layer region in contact with the lower layer; It is characterized by being made up of layers.

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.

Furthermore, in the lower layer, aluminum atoms (Al),
By containing silicon atoms (Si), especially hydrogen atoms (H) in a non-uniform distribution in the layer thickness direction, the injection of charges (photocarriers) between the aluminum support and the upper layer is improved. Furthermore, since the structural continuity of the constituent elements between the aluminum support and the upper layer is improved, image characteristics such as roughness and spots are improved, halftones appear clearly, and High resolution,
High quality images can be stably and repeatedly obtained.

Furthermore, image defects and non-contamination may occur due to relatively short-term impact mechanical pressure applied to electrophotographic light-receiving members.
It prevents the occurrence of peeling of the 3i (If,
It can alleviate the stress caused by the difference in the thermal expansion coefficient of the 5t (It, .

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

Furthermore, in the present invention, germanium atoms (Ge) and tin atoms (
By containing at least one of Sn), the adhesion between the upper layer and the lower layer is further improved, and the occurrence of image defects and peeling of the Non-8i (H,X) film is prevented. prevents this and improves durability. Furthermore, even if long-wavelength light such as a semiconductor laser is used as a light source for image exposure in an electrophotographic device, the long-wavelength light that cannot be absorbed between the surface side of the lower layer and the lower layer side is highly efficient. Since the light is absorbed, interference phenomena caused by reflection of long wavelength light at the interface between the upper layer and the lower layer and/or the surface of the support can be significantly prevented, and the image quality can be dramatically improved.

Note that 1. Although it is mentioned that aluminum atoms and silicon atoms are contained non-uniformly in the layer thickness direction, and that hydrogen atoms are also contained, there is no mention of how the hydrogen atoms are contained, and this does not correspond to the present invention. are clearly distinguishable.

[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. ) and hydrogen atom (H)
The lower layer 103 is composed of Non-5i (H,
and an upper layer 104 containing at least one of Sn atoms (Ge) and tin atoms (Sn). Top layer 104 has a free surface 105.

Aluminum support 101 used in the present invention
An aluminum alloy is used as the material. There are no particular limitations on the alloy components including the substrate aluminum in the aluminum alloy of the present invention, and the types, compositions, etc. of the components can be arbitrarily selected. Therefore, the aluminum alloy of the present invention has Japanese Industrial Standards (J
IS), pure aluminum type, A1-Cu type, Al-Mn type, At -5i series, Al-Mg series, Al-
Alloys with compositions such as Mg-3i series, Al-Zn-Mg series, etc.
Al-Cu-Mg system (duralumin, super duralumin, etc.), A1-Co-5i system (Lautal, etc.), A1-Cu-
Contains Ni-Mg type (Y alloy, RR gold alloy), aluminum powder sintered body (SAP), etc.

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

Examples of pure aluminum include Moon 5I100, S
i and Fe 1.0% by weight or less, Cu O, 05-0
．． 20% by weight, Mn 0.05% by weight or less, Zn
O, 10% by weight or less, A1, 99.00% by weight or more.

As an Al-Cu-Mg system, for example, the month 52017,
SiO, 05-0.20% by weight, Fe 0.7% by weight or less, Cu 3.5-4.5% by weight, Mn 0.40-1.
0% by weight, Mg 0.40-0.8% by weight, Zn
0.25 weight 1% or less, CrO, 10 weight% or less, A
I The remainder is mentioned.

As the At-Mn system, for example, JIS3003, Si
0.6% by weight or less, Fe0.7% by weight or less, CuO
, 05-0.20% by weight, In 1.0-1.5% by weight
, ZnO, 10% by weight or less, and the remainder A1.

As the Al-3i system, for example, JIS4032 Si
11.0 to 13.5% by weight, Fe 1.0% 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, Al
The remainder is mentioned.

As the A1-Mg system, for example, seal 55086, Si0
．． 40% by weight or less, Fe O, 50% by weight or less, Cu
O, 10% by weight or less, Mn 0.20-0.7% by weight, Mg 3.5-4.5% by weight, Zn O, 25
Weight% or less, CrO, 05-0.25% by weight, Ti
O, 15% by weight or less, and the remainder AI.

Furthermore, Si 0.50% by weight or less, FeO,
25% by weight or less, CuO, 04-0.20% by weight,
Mn O, 01-1.0% by weight, Mg O, 5-10
Weight%, 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, 1.0 cc or less per 100 grams of H, Al, and the balance A1.

Furthermore, Si 0.12% by weight or less, Fen
, 15% by weight or less, MnO, 30% by weight or less, M
g O, 5-5.5% by weight, Zn O, 01-1.0
Weight % or less, Cr O, 20 weight % or less, Zr O
, 1 to 0.25% by weight or less, and the remainder A1.

As the Al-Mg-5i system, for example, J l56063
, SiO, 20-0.6% by weight, FeO, 35% by weight or less, Cub, 10% by weight or less, Mn 0.1
0% by weight or less, MgO, 45-0.9% by weight, Zn
O, 10% by weight or less, Cr O, 10% by weight or less, T
Examples include i O, 10% by weight or less, and the remainder A1.

As the Al-Zn-Mg system, for example, JIS7NO1, 5jO 130% by weight or less, Fe O, 35% by weight or less, Cu O, 20% by weight or less, Mn 0.20~
0.7% by weight, Mg 1.0-2.0% by weight, Zn 4
．． (1 to 5.0% by weight, CrO, 30% by weight or less,
Ti 0.20% by weight or less, Zr O, 25% by weight
The following examples include vo, io weight percent or less, and the remainder of AI.

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

In the present invention, the shape of the aluminum support 101 is as follows:
It can be in the shape of a cylindrical or plate-like endless belt with a smooth or uneven surface, and its thickness is determined as appropriate to form a desired electrophotographic light-receiving member.
When flexibility is required as a light-receiving member for electrophotography, it can be made as thin as possible within the range where the function as a support is fully exhibited.However, due to the manufacturing of the support and In terms of handling and mechanical strength, it is usually 1
It is assumed to be 0 μm or more.

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

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

Further, as another method for eliminating image defects caused by interference fringe patterns when coherent light such as laser light is used, an uneven shape formed by a plurality of spherical trace depressions may be provided on the surface of the support.

That is, the surface of the support has irregularities smaller than the resolving power required for electrophotographic light-receiving members, and the irregularities are
This is due to multiple spherical trace depressions.

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

L layer The lower layer in the present invention is composed of an inorganic material containing a small amount of aluminum atoms (A1), silicon atoms (Si), hydrogen atoms (I+), and halogen atoms (X) as constituent elements. Atomic (CNO) to adjust durability accordingly
, ) may contain an atom (Mc) that adjusts image quality.

Aluminum atoms (AI), silicon atoms (Si), 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). There are parts where the distribution concentration is uneven.However, in the in-plane direction parallel to the surface of the support, it is evenly distributed and evenly contained, which makes the properties uniform in the in-plane direction. It is also necessary from this point of view.

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 uniform distribution state, or it may be contained evenly in the entire layer area of the lower layer,
There may be a portion where the content is non-uniformly distributed in the layer thickness direction. However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary to have a uniform distribution and no bias (it is also necessary to make the properties uniform in the in-plane direction). .

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

In the electrophotographic light-receiving member of the present invention, as described above, aluminum atoms (Al) 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. It is desirable to

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) and an atom that adjusts image quality (Mc') contained as necessary, in the layer thickness direction.

In Figures 3 to 8, the horizontal axis is the aluminum atom (
Al) (hereinafter abbreviated as "atom (Al) J") 1 halogen atom (X) (hereinafter abbreviated as "atom (X)"),
Atom (CNO,) that adjusts durability (hereinafter referred to as [atom (CN
(abbreviated as OC) J), atoms that adjust image quality (MC) (
Hereinafter, abbreviated as [atom (M,)J, atom (AI) and atom (
X), atom (CNOc), and atom (Mc) are collectively abbreviated as "atom (AX)J."However, atom (AI) and atom (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, and to is tT indicates the position of the end surface of the lower layer on the support side, and tT 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 formed from the tII side toward the t7 side.

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) is at position 1. From there, the concentration is C31 up to position t31.
A distribution state is formed in which the concentration Cjl decreases in a linear function from the position t31 to the position t□, and reaches the concentration C32 at the position t7.

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

In the example shown in FIG. 5, the distribution concentration C of the contained atoms (AX) is the concentration Ca from position t to position
A distribution state is formed in which the concentration gradually and continuously decreases from 1 to 1 and reaches a concentration C62 at 1 ItT.

In the example shown in FIG. 6, the distribution concentration C of the contained atoms (AX) is the concentration C61 from position t8 to position tg+.
Take a constant value such that the place fit t e + the place M
Until tt, the concentration decreases linearly from C62, forming a distribution state in which the concentration Css is reached at position ty.

In the example shown in FIG. 7, the distribution concentration C of the contained atoms (AX) is the concentration cy+ from the position tll to the position tel.
The concentration takes a constant value from position a t t + to position t1. A distribution state is formed in which the concentration gradually and continuously decreases from Ctz and reaches the concentration Cts at the position t7.

In the example shown in FIG. 8, the distribution concentration C of the contained atoms (AX) is the concentration C1l from position t to position jt.
The concentration C gradually decreases continuously from
A distribution state of 8□ is formed.

As described above with reference to FIGS. 3 to 8, some typical examples of the distribution state of atoms (AI) contained in the lower layer in the layer thickness direction, in the present invention, on the support side,
The interface t contains silicon atoms (Si) and hydrogen atoms (H) and has a portion with a high distribution concentration C of atoms (Al). In this case, 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 CmaX of the distribution concentration of atoms (A1) is preferably 10 at% or more, more preferably 30 at%
As mentioned above, it is desirable to form layers so that the distribution state is optimally 50 atomic % or more.

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

In FIGS. 9 to 16, the horizontal axis represents silicon atoms (S
i), hydrogen atom (H), halogen atom (X), atom (C
NOc), atoms (Mc) (hereinafter collectively abbreviated as "atoms (SHX)J").

However, silicon atoms (Si), hydrogen atoms (H), and atoms (X
), the distribution state of atoms (CNOc), and atoms (M, ) in the layer thickness direction may be the same or different), and the vertical axis indicates the layer thickness of the lower layer, and I8 indicates the position of the end face of the lower layer on the support side, and t 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 t.

The layer is formed from the side toward the tT 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) is at position t. A distribution state is formed in which the concentration increases numerically from CG+ for one hour up to position t91, and takes a constant value of concentration C'+2 from position 1*+ to position t7.

In the example shown in FIG. 10, the contained atoms (S HX
) forms a distribution state in which the concentration C increases linearly from the concentration C+o+ from the position t8 to the position t't, and becomes the concentration C1°2 at the position 11.

In the example shown in FIG. 11, the atoms contained (SHX)
The distribution concentration C gradually and continuously increases from the concentration CI I + from the position tB to the position 11, and forms a distribution state in which the concentration C112 is reached at the position tT.

In the example shown in FIG. 12, the atoms contained (SHX)
The distribution density C of is at position t. From position t12. The concentration increases numerically for one hour from the concentration CI21 until reaching the positions t, 2. A distribution state is formed in which the concentration becomes C122 at the position t2° and a constant value of the concentration CI23 from the position t2° to the position t1.

In the example shown in FIG. 13, the atoms contained (SHX)
The distribution concentration C gradually and continuously increases from the concentration C1,1 to the position t13 from the position tlI to the position t31.
1, the density becomes C1, 2, and from position t13 to position 11, the density becomes C33, forming a distribution state that takes a constant value.

In the example shown in FIG. 14, the contained atoms (SHX)
The distribution concentration C gradually and continuously increases from the concentration C841 from the position to to the position t7, and forms a distribution state in which the concentration becomes CI4□ at the position 11.

In the example shown in FIG. 15, the contained atoms (SHX)
The distribution concentration C of is substantially zero from position tn to position t151 (here, substantially zero means the case where the amount is less than the detection limit, and the meaning of "substantially zero" hereinafter is also the same). )
The concentration C1,1 gradually increases from C1,1 at position t1,1.
Therefore, the concentration C is from position t151 to position 11.
A distribution state is formed that takes constant values of 1 and 2.

In the example shown in FIG. 16, the contained atoms (S HX
) forms a distribution state in which the distribution concentration C gradually increases from substantially zero from position tIl to position 11, and reaches the concentration C461 at position 11.

As described above with reference to FIGS. 9 to 16, some typical examples of the distribution state of silicon atoms (S i ) and hydrogen atoms (H) contained in the lower layer in the layer thickness direction, the present invention In this case, aluminum atoms (A
1), and contains silicon atoms (Si) and hydrogen atoms (H
), and at the interface tT, the distribution concentration C is considerably higher than that on the support side. A preferred example is formed when silicon atoms (Si) are provided in a layer.
, the maximum value Cmax of the distribution concentration of the sum of hydrogen atoms (H) is:
It is desirable that the layer be formed in such a manner that a distribution state can be achieved such that the content is preferably 0 atomic % or more, more preferably 30 atomic % or more, and optimally 50 atomic % or more.

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

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

As the halogen atom (X), a fluorine atom (F)
, chlorine atom (C1), bromine atom (Br), iodine atom (
1) 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 (S i ), 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 appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 4 x 10' atomic ppm, more preferably 10~3x105 atomic ppm
, most preferably lXl0'' to 2X10' atoms ppm.

Atom (
CNOc), carbon atom (C), nitrogen atom (N)
, an oxygen atom (0) is used. In the present invention, carbon atoms (
C) and/or contain nitrogen atoms (N) and/or oxygen atoms (0) to mainly improve charge injection properties between the aluminum support and the upper layer and/or in the lower layer. It is possible to obtain the effect of improving charge migration properties and/or the effect of improving the adhesion between the aluminum-based support and the upper layer.

Furthermore, the effect of controlling the forbidden band width can also be obtained in a layer region in which the content of aluminum atoms (AI) is small in the lower layer. The content of durability adjusting atoms (CN Oc ) contained in the lower layer is preferably 1×1.
0' to 5X10' atomic ppm, more preferably 5X10
'~4X10' atoms 1) 1) m% optimally lXl0'~
Preferably, the amount is 3×10” atomic ppm.

Atoms (M
c), atoms and children belonging to Group II of the periodic table (hereinafter referred to as “
(hereinafter abbreviated as "Group V atoms"), atoms belonging to Group V of the periodic table excluding nitrogen atoms (N) (hereinafter abbreviated as "Group V atoms"), atoms belonging to Group V of the periodic table excluding nitrogen atoms (0), Atoms belonging to group Ⅰ (hereinafter abbreviated as ``group Ⅰ atoms'') are used. Specifically, the Group Ⅰ atoms include B (boron), Aj (aluminum), Ga (gallium), In (indium), and T.
I (thallium), etc., especially B.

AI and Ga are preferred. Specifically, the Group V atoms include P (phosphorus), As, (arsenic), and sb (antimony).
, Bi (bismuth), etc., and P and As are particularly suitable. Specifically, as a group ■ atom, S (sulfur)
, Se (selenium), Te (tellurium), Po (boronium), etc., especially S.

Se is preferred. In the present invention, the lower layer mainly contains a group Ⅰ atom, a group V atom, or a group ① atom as an atom CM,') that adjusts the image quality, so that the The effect of improving the charge injection property and/or the effect of improving the charge running property in the lower layer can be obtained. Furthermore, it is possible to obtain the effect of controlling the conductivity type and/or conductivity in a layer region in which the content of aluminum atoms (AI) is low in the lower layer. The content of atoms (Me) that adjusts the image quality contained in the lower layer is preferably lXl0-3 to 5X10' atoms ppml, more preferably lXl0-'' to IX10i atoms ppm, most preferably 1xlO. -' to 5xlO'' atoms ppm.

In the present invention, the lower layer composed of Al5i)I is
For example, it is created by a vacuum deposition film formation method similar to that for the upper layer described later, with numerical conditions of film formation parameters set appropriately so as to obtain desired characteristics. 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, etc.), ECR-CVD method, sputtering method, vacuum evaporation method, ion blating method, In the photo-CVD method, active species (A) are generated by decomposing the raw material gas, and active species (B) are generated from the film-forming chemicals that chemically interact with the active species (A). ) are separately introduced into a film forming space for forming a deposited film, and a material is formed by chemically reacting them (hereinafter abbreviated as "rHRCVD method"), a raw material gas of the material, A method of forming a material by introducing halogen-based oxidizing gases having the property of oxidizing the raw material gas separately into a film forming section for forming a deposited film and causing a chemical reaction between them ( It can be formed by a number of thin film deposition methods such as the rFOcVD method (hereinafter abbreviated as "rFOcVD method"). These thin film deposition methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be produced. It is relatively easy to control the conditions for manufacturing electrophotographic light-receiving members with specific characteristics, and hydrogen atoms can be easily introduced in addition to aluminum atoms and silicon atoms. Discharge method, sputtering method, ion blating method, HRC
VD method and FOCVD method are preferred. These methods may be used in combination within the same device system. For example, by the glow discharge method, A I S i II
In order to form the lower layer consisting of, basically, a raw material gas for A1 supply that can supply aluminum atoms (A1), a Si supply gas that can supply silicon atoms (Si), and a hydrogen H supply gas capable of supplying atoms (I4);
An X supply gas capable of supplying halogen atoms (X), a CN0c supply gas capable of supplying atoms (CNOc) for adjusting durability as necessary, and atoms (Mc) for adjusting image quality as necessary. A Me supplying gas capable of supplying Me is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber, and a predetermined support installed at a predetermined position is AIS on the body surface
A layer consisting of iII may be formed.

In order to form a lower layer composed of A I S i H by the HRCVD method, basically a raw material gas for supplying A1 that can supply aluminum atoms (AI) and silicon atoms (Si) are supplied. Si supply gas to obtain Si, X supply gas capable of supplying halogen atoms (X), and C capable of supplying atoms (CNO, C) for adjusting durability as necessary.
The NO, supply gas and the Mc supply gas, which can supply atoms (Mc) for adjusting the image quality as necessary, are supplied separately or together as necessary in a deposition chamber whose interior can be reduced in pressure. By introducing the gas at a desired pressure into the activation space provided in the previous stage and causing a glow discharge in the activation space or by heating, active species (A) are generated and hydrogen atoms (H) are generated. A raw material gas for H supply that can supply H is similarly introduced into another activation space to generate active species (B).
A) and the active species (B) may be separately introduced into the deposition chamber to form a layer of Al5iH on the back surface of a predetermined support which is then swaged and placed at a predetermined position.

In order to form a lower layer composed of AlSiH by the FOCVD method, basically aluminum atoms (
A1 supply source gas capable of supplying A1), Si supply gas capable of supplying silicon atoms (Si), H supply gas capable of supplying hydrogen atoms (H), and halogen atoms (X
), a CN0c supply gas that can supply atoms (CNOc) that adjust durability as necessary, and atoms (Mc) that adjust image quality as necessary. M. Introducing supply gas at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, separately or together as necessary, and further introducing halogen (X) gas separately from the source gas. Gases are introduced into the deposition chamber at a desired pressure, and these gases are chemically reacted in the deposition chamber to form a layer of AISiIt on the surface of a predetermined support that has been placed in a predetermined position in advance. All you have to do is form.

When forming by sputtering method, for example, Ar,
A target made of A1 in an atmosphere of an inert gas such as He or a mixed gas based on these gases,
Hydrogen atoms (H
) and a raw material gas for H supply that can supply halogen atoms (
X supply gas that can supply X), CN0e supply gas that can supply atoms (CNOc) that adjust durability as necessary, and atoms (Me) that adjust image quality as necessary.
A Mc supply gas that can supply aluminum atoms (
By introducing a raw material gas for A1 supply capable of supplying A1) and/or a Si supply gas capable of supplying silicon atoms (Si) into a deposition chamber for sputtering and forming a plasma atmosphere of the desired gas. will be accomplished.

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) and silicon atoms (Si
), a hydrogen atom (H), a halogen atom (father), an atom that adjusts durability (CNOc) contained as necessary, and an atom that adjusts image quality (MC) (hereinafter, these will be collectively referred to as "atoms ( By changing the distribution concentration C of ASH) (abbreviated as
In the case of glow discharge method, HRCVD method, and FOCVD method, to form a layer having a
This is accomplished by introducing a raw material gas for supplying atoms (A S H) whose distribution concentration is to be changed into the deposition chamber while changing its gas flow rate appropriately according to a desired rate of change curve.

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

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

The second method is to use a sputtering target such as Al
If a target containing a mixture of A1 and Si is used, this can be done by changing the mixing ratio of A1 and Si in advance in the layer thickness direction of the target.

Substances that can be used as the raw material gas for supplying A1 used in the present invention include AlC1m, AlBr3°AI 1.
, AI (CH,), CI, AI (CH3),.

AI(OCH3),,AI(C,H,)3. AI (Q
Cs Ha) s, AI (i-C4H9)3
, AI(i-C3H7)1. AI (C8Hff)3
．． AI(OC4He)s etc. can be cited as one that can be effectively used. Further, these raw material gases for supplying Al may be diluted with gases such as H2, He, Ar, Ne, etc. as necessary.

Substances that can be used as the Si supply gas used in the present invention include S i H4, S i 2 Ha, and S i
Gaseous or gasifiable silicon hydride (silanes) such as aHs, S 14H1+1, etc. can be used effectively, and they also have advantages such as ease of handling during layer creation work and good St supply efficiency. S I H4゜S
12 Hs is preferred. In addition, these raw material gases for Si supply may be converted to I(2, H
It may be used after being diluted with a gas such as e, Ar, or Ne.

Effective halogen supplying gases used in the present invention include many halogen compounds, such as gaseous or gasified halogen gases, halides, 710 intergen compounds, halogen-substituted silane derivatives, etc. Preferred examples include /'% rogen 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 10-gen atom, can also be mentioned as an effective compound in the present invention.

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CIF, ClF3. BrFa, Br
F5+HF3. IF? +Interhalogen compounds such as ICI and IBr can be mentioned.

Preferred examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with 710 Ken atoms, include silicon halides such as SiF4,5i2F, and 5iC14,5xBr.

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 its use, a lower layer consisting of A I S i H containing 10-gen atoms can be formed on the desired support.

When forming a lower layer containing norogen atoms according to the glow discharge method or HRCV D method, basically,
For example, a lower layer can be formed on a desired support by using halogenated silicon as a Si supply gas, but in order to make it easier to introduce 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.

Moreover, each gas may be used not only as a single species but also as a mixture of multiple species with a predetermined whitening effect.

In the present invention, the above-mentioned halogen compounds or silicon compounds containing nitrogen are effectively used as the halogen atom supply gas, but HF and HCI are also used.

Hydrogen halides such as HBr, HI, SiH, F.

5i) 12 F2+ 5iHFi, 5iHz I2,
5iH2C12, S iHc]3+ S 1H2Br
Gaseous or gasifiable substances such as halogen-substituted silicon hydrides such as 2+5iHBr can also be mentioned as effective raw materials for forming the lower layer. Among these substances, hydrogen atoms containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, into the layer at the same time as forming the lower layer. Therefore, it is used as a suitable halogen supply gas in the present invention.

In order to structurally introduce hydrogen atoms into the lower layer, in addition to the above, FI2, S r Ha , S 12 Ha,
Sis Ha, 5i4H+. This can also be carried out by causing a discharge by causing silicon hydride such as and silicon or a silicon compound for supplying Si to coexist in a deposition chamber.

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

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 atoms must be added during layer formation. (C) Raw material for introduction or nitrogen atom (N)
The raw material for introducing oxygen atoms (0) 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 lower layer. Carbon atom (C
) Materials that can be used as a raw material for introduction, a raw material for introducing nitrogen atoms (N), or a raw material for introducing oxygen atoms (0) are gaseous at room temperature and pressure, or at least under layer formation conditions. It is desirable to use a material that can be easily gasified under the conditions.

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

Specifically, the saturated hydrocarbons include methane (CH4,
Ethane (C,H,), Propane (C.

H@), n-butane (nc4HIO) l-pentane (C,
H,, ), ethylene hydrocarbons include ethylene (C
, H4), propylene (C,H,).

Butene 7/1 (C4Hs) + Butene 2 (CB
F6), isobutylene (C4H,'), pentene (C,
H. ), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C,H4), butyne (C,H, ), and the like.

As a raw material gas containing Si, C, and H as constituent atoms, 5
Alkyl silicides such as i(CH3)41Si(C2H5)4 can be mentioned.

In addition to this, in addition to introducing carbon atoms (C), halogen atoms (X) can also be introduced, so CF, CCI4
．． Examples include halogenated carbon gases such as CH3CF.

Raw materials that can be effectively used as raw material gases for introducing nitrogen atoms (N) include nitrogen (N2>,
Ammonia (NH,).

hydrazine (H,NNH,), hydrogen azide (HN,),
Gaseous or gasifiable nitrogen such as ammonium azide (NH,N, ), nitrogen compounds such as nitrides and azides may be mentioned.

In addition to this, nitrogen trifluoride (F,
N), nitrogen tetrafluoride (F4N2), and other halogenated nitrogen compounds.

Starting materials that can be effectively used as raw material gas for introducing oxygen atoms (0) include, for example, oxygen (0,),
Ozone (0,), -nitrogen oxide (No), nitrogen dioxide (N
o, ), -nitrogen dioxide (NaO), nitrogen sesquioxide (N
20. ), trinitric oxide (N, O,)rnitric oxide (
N, 0. ).

Nitrogen dioxide (NO2), disiloxane (H,5iO8iH,), )disiloxane (Hs SiO8t H20SiHs) whose constituent atoms are a silicon atom (S i), an oxygen atom (0), and a hydrogen atom (H) Lower siloxanes such as □ can be mentioned.

In order to structurally introduce atoms (Me) that adjust image quality into the lower layer, for example, group Ⅰ atoms, group Ⅰ atoms, or group Ⅰ atoms, a method for introducing group Ⅰ atoms during layer formation The raw material for introducing Group V atoms or the raw material for introducing Group I 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 (III) atoms, a raw material for introducing group V atoms, or a raw material for introducing group (III) atoms may be gaseous at room temperature and pressure, or at least under layer-forming conditions. It is desirable to use a material that can be easily gasified. Specifically, as a raw material for introducing such group III atoms, for introducing boron atoms,
B2H,,B4H,. , B, H + B 5 Hl
l+B 6H,. , B, H, □, boron hydride such as B6H14, BF3. BCl3. Examples include boron halides such as BBrs. In addition, AlCl3. GaC]s
, Ga (CH3), , InCH8, TlC11, 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.
, next to hydrogen ratio such as P 284, PH41, PF,,
PF,, Pct,, PCl,, PBr,, PBrs, P
Examples include halogen ratios such as I3. In addition, A s
H3, A s F s + A 5C1a , AsBr
a, AsF5, SbH3, SbF3, 5bF
s + 5bCI3, 5bCls,
BiH3, B1C1, B1Br3, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

Hydrogen sulfide (H2
S), SF4. SF,,So,.

5o2F,,CO8,C3,,CH,SHC.

H,31(,C,H4S,(CH3)25(C.

Examples include substances in a gaseous state or capable of being gasified, such as H, )28. In addition, SeH2, SeF, l, (CH3)
2Se, (C2Hs)2Se.

TeH,, TeFs, (CH3)2Te, (C2H
s) 2 Te, etc., or substances that can be gasified.

In addition, H=, He is used as a raw material for introducing atoms (Mc) to control these image quality 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 1 preferably 0.01 to 1 μm 1 optimally 0.01 to 1 μm 1 .
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 support is the aluminum atom (A1) of the lower layer.
This is a region in which the content of aluminum atoms (AI) is 95% or less of the content of aluminum atoms (AI) in the aluminum-based support.

This is because in a composition region where the content of aluminum atoms (AI) exceeds 95% of the content of aluminum atoms (Al) 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 achieve the object of the present invention and to form a lower layer made of Al5iH having stable properties, it is necessary to appropriately set the gas pressure in the deposition chamber and the temperature of the support as desired.

The gas pressure in the deposition chamber is appropriately selected in the optimum range according to the layer design, but in normal cases it is between lXl0-' and 10Torr1.
Preferably lXl0-'~3Torr, optimally I
It is preferable to set it as X10-'~ITorr.

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

In the present invention, when forming the lower layer made of Al5iH by the glow discharge method, the optimal range of discharge power supplied into the deposition chamber is selected as appropriate according to the layer design, but in normal cases, the discharge power is 5X10-' to IOW/cd. , preferably 5
X10-'~5W/crt? , optimally I
It is desirable to set it to 0-'' to 2 x 10-'W/crd.

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 optimal values for the lower layer forming factors based on mutual and organic relationships in order to form a lower layer having desired properties.

-Made by L part The upper layer in the present invention is Non-3i (H.

X) and has desired photoconductive properties.

In the present invention, at least the layer region of the upper layer in contact with the lower layer contains germanium atoms and/or tin atoms, and if necessary, atoms (M) and/or carbon atoms (C) and /or nitrogen atom (N
) and/or an oxygen atom (0). In addition, in other layer regions of the upper layer, atoms controlling conductivity (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge), tin atoms ( S
It may contain at least one of n). Especially in the layer region near the free surface side of the upper layer, carbon atoms (
C), a nitrogen atom (N), and an oxygen atom (0).

Germanium atoms (Ge) and/or tin atoms (
Sn) and/or atoms controlling conductivity (M) and/or carbon atoms (C) contained as necessary
and/or the nitrogen atoms (N) and/or the oxygen atoms (0) may be uniformly distributed throughout the layer region, or may be uniformly contained within the layer region; There may be a portion where the content is non-uniformly distributed in the layer thickness direction. However, in any case, it is necessary that the content be uniformly distributed and evenly distributed in the in-plane direction parallel to the surface of the support, in order to make the properties uniform in the in-plane direction. .

Atoms that control conductivity (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), germanium atoms (
Ge), tin atom (S n), the conductivity controlling atom (M), carbon atom (C), nitrogen atom (N), oxygen atom (o), germanium Atoms (Ge) and tin atoms (Sn) may be uniformly distributed in the layer region, or they may be uniformly contained in the layer region, but they may There may be a portion where the content is non-uniformly distributed.However, in any case, the content must be uniformly distributed in the in-plane direction parallel to the surface of the support. However, it is also necessary from the point of view of making the characteristics uniform in the in-plane direction.

In addition, atoms (M) that control conductivity (hereinafter referred to as "atoms (M)"
(hereinafter referred to as "layer region (M
)”) and a layer region containing carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (O) (hereinafter abbreviated as “atoms (CNO)J”) (hereinafter “
a layer region in contact with at least the lower layer of the upper layer containing germanium atoms (Ge) and/or tin atoms (Sn) (hereinafter abbreviated as "atoms (GS)J)" (hereinafter abbreviated as "layer region (GS,) J") may be substantially the same layer region,
At least a part of the surface side of the layer region (GSIl) may be shared.

In addition, a layer region containing atoms (GS) other than the layer region (GS,) (hereinafter abbreviated as "layer region (GS,) J", and the layer region (GS,) and layer region (GS,) are collectively referred to as "layer region (GS,)"). "Layer area (
GS) J), layer region (M), and layer region (C
NO) may be substantially the same layer region, or may share at least a part of each layer region,
It is not necessary that the respective layer regions are 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, layer region (M), layer region (CNo'), and layer region (GS) will be referred to as "layer region (Y)," and atoms (M), atoms (CNO), and atoms (GS) will be referred to as "layer regions (Y)." on behalf of"
Atom (Y)”. Therefore, FIGS. 17 to 36
The figure shows a typical example of the distribution state of atoms (Y) contained in the layer region (Y) in the layer thickness direction. ), layer region (GS
) are substantially the same layer regions, the layer region (Y)
is placed in a single unit in the upper layer, and if the layer area is not substantially the same, multiple units in the layer area (Y) are placed in the upper layer)
.

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

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

In the example shown in FIG. 17, the distribution concentration C of the contained atoms (Y) is the concentration C1 from position t to position 11.
A distribution state is formed in which the concentration gradually and continuously increases from 7, to reach a concentration C17 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 C3, . C,2, forming a distribution state in which the concentration takes a constant value of C+aa from position t3,1 to position t7.

In the example shown in FIG. 19, the distribution concentration C of the contained atoms (Y) has a constant value of concentration C191 from position te to position t3,1, and from position t1.1 to position 11.
The concentration increases gradually and continuously from C1,1 until it reaches ft+*z, and reaches the concentration C1112 at position t1112.
A distribution state is formed that takes a certain value.

In the example shown in FIG. 20, the distribution concentration C'It of the contained atoms (Y) is a constant value of C2° from position t to position t201, and from position t2°1 to position t2 A distribution state is formed in which the concentration is a constant value of C2.degree.2 up to the point t2.degree., and the concentration is a constant value of C2.8 from the position t2.degree. to the position t7.

In the example shown in FIG. 21, the distribution concentration C of the contained atoms (Y) forms a distribution state in which the concentration C2□ is a constant value from position t6 to position 11.

In the example shown in FIG. 22, the distribution concentration C of the contained atoms (Y) is from position t to position t211, which is the concentration C2.
21, and the position t, 2. A distribution state is formed in which the concentration gradually and continuously decreases from C222 until reaching position 11, and becomes C2□3 at position f&tt.

In the example shown in FIG. 23, the distribution concentration C of the contained atoms (Y) is as follows:
A distribution state is formed in which the concentration gradually and continuously decreases from 2$1 to a concentration C2,2 at position 11.

In the example shown in FIG. 24, the distribution concentration C of the contained atoms (Y) is the concentration C2 from the position ta to the position t241.
41, and the position t24. The distribution concentration C gradually and continuously decreases from C24□ until reaching position tr, and at position 11, the distribution concentration C becomes substantially zero (here, substantially zero means that the amount is below the detection limit. The meaning of "substantially zero" is also the same).

In the example shown in FIG. 25, the distribution concentration C of the contained atoms (Y) is the concentration C2 from position t8 to position 11.
A distribution state is formed in which the distribution concentration C gradually and continuously decreases from B+ 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 t261, which is the concentration C2.
61, and the position t26. The concentration C3,1 decreases linearly until it reaches position 11, and the position [
1, a distribution state is formed such that the concentration is C26.

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

In the example shown in FIG. 28, the distribution concentration C of the contained atoms (Y) is from position t8 to position t281.
2m! The position t28. From position tT
A distribution state is formed in which the concentration decreases in a linear function from the concentration C25l until reaching the concentration C28□ at the position t1.

In the example shown in FIG. 29, the distribution concentration C of the contained atoms (Y) is the concentration C2 from the position tn to the position tT.
, 1 gradually and continuously decreases, forming a distribution state in which the concentration C2,2 is reached at position t7.

In the example shown in FIG. 30, the distribution concentration C of the contained atoms (Y) is from position te to position t. Concentration C3 up to 1
゜, takes a constant value, and from position j 301 to position tT
The concentration decreases linearly from C302 until it reaches position 1.
1, a distribution state is formed such that the concentration is C3°.

In the example shown in FIG. 31, the distribution concentration C of the contained atoms (Y) increases gradually and continuously from the concentration C3□ from position tn to position t and 1°, and at position t3□, the concentration C increases gradually and continuously. C312, forming a distribution state in which the concentration takes a constant value C81 from position t, 11 to position t7.

In the example shown in FIG. 32, the distribution concentration C of the contained atoms (Y) gradually and continuously increases from the concentration C321 from the position tn to the position t'r, and reaches the concentration C32□ at the position 11. The distribution state is formed as follows.

In the example shown in FIG. 33, the distribution concentration C of contained atoms and atoms (Y) is at position t. It gradually increases from substantially zero (here, substantially zero means that the amount is less than the detection limit, and the meaning of "substantially zero" hereinafter is also the same) until it reaches position t33°. Position t33. The concentration becomes C3,1 at t8,1, and the concentration C3 from position t8,1 to position 11.
A distribution state is formed that takes a constant value of 32.

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 1t□, and at position 11 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) varies from position tll to position t8. .

A distribution state is formed in which the concentration increases linearly from C3,1 until reaching , and takes a constant value of concentration C3,2 from position t381 to position tT.

In the example shown in FIG. 36, the distribution concentration C of the contained atoms (Y) is from position t to position 1T, the concentration C36,
-increasing numerically from - to the concentration C3 at position t7.
62 is formed.

Examples of the atom (M) that controls the conductivity include so-called impurities in the semiconductor field. (abbreviated as "group atom") or n
Periodic table V excluding the nitrogen atom (N) which gives type conductivity properties
(hereinafter abbreviated as "Group V atoms") and atoms belonging to Group ■ of the periodic table, excluding oxygen atoms (0) (hereinafter abbreviated as "Group V atoms")
Hereinafter abbreviated as "Group I atoms") will be used.

Specifically, the Group Ⅰ atom is B (boron).

AI (aluminum), Ga (gallium), In(
Indium), TI (thallium), etc., especially B, A
I, Ga are preferred. Specifically, the Group V atoms include P (phosphorus) and As (arsenic).

Sb (antimony), Bi (bismuth), etc.

In particular, P and As are suitable. As group ■ atoms,
Specifically, there are S (sulfur), Se (selenium), Te (tellurium), Po (boronium), etc., with S and Se being particularly preferred. In the present invention, the conductivity type and/or conductivity is mainly controlled by containing a group (I) atom, a group V atom, or a group (IV) atom as an atom (M) that controls conductivity in the layer region (M). It is possible to obtain the effect of controlling and/or the effect of improving the charge injection property between the layer region (M) and layer regions other than the layer region (M) of the upper layer. Atoms that control conductivity contained in the layer region (M) (
The content of M) is preferably 1X10-' to 5X1
0' atoms ppm.

More preferably lXl0-” to lX104 atoms ppm1
The optimal range is preferably 1xlO-' to 5xlO3 atomic ppm. In particular, when the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) described later in the layer region (M) is 1 x 103 atomic ppm or less, the layer region (M) The contained atom (M) that controls conductivity is preferably lXl0-'
It is desirable that the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) exceeds I x 10' atomic ppm. The content of the atoms (M) that controls the properties is preferably 1X10-' to 5X10' atoms ppm
It is desirable that this is done.

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). The layer area of the upper layer (
It is possible to obtain the effect of improving the adhesion between layer regions other than CNO). The content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) contained in the layer region (CNO) is preferably 1 to 9.
X10' atoms ppm 1 more preferably lXl0' to 5X
It is desirable that the content be 10' atomic ppm, optimally 1X10" to 3X10' atomic ppm. In particular, when aiming at high dark resistance and/or high hardness, it is preferably 1x103
It is desirable to set it to ~9x106 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, and in particular, to control the spectral sensitivity, and in particular to use a semiconductor laser or the like as an image exposure source of an electrophotographic device. The effect of improving the long wavelength light sensitivity when using long wavelength light and/or the effect of preventing the appearance of interference phenomena, and/or the effect of improving the adhesion between the layer region (GSll) and the lower layer and/or Alternatively, it is possible to obtain the effect of improving the adhesion between the layer region (GS) and the layer region other than the layer region (GS) of the upper layer. The content of germanium atoms (Ge) and/or tin atoms (S n ) contained in the layer region (GS) is preferably 1 to 9.5 x 1011 atoms 1) 9 m%
More preferably, it is 1×10 2 to 8×10 6 atomic ppm, most preferably 5×10” to 7×10 8 atomic ppm.

Further, hydrogen atoms (H) contained in the upper layer in the present invention
And/or halogen atoms (X) can compensate for dangling bonds of silicon atoms and improve layer quality. Hydrogen atoms (H) contained in the upper layer, or hydrogen atoms (
The total content of H) and halogen atoms (X) is preferably I
The content of halogen atoms (X) is preferably 1 to 4.
It is desirable that the amount is x108 atomic ppm. In particular, when the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) described above in the upper layer is 3X10' atoms ppm or less, hydrogen atoms (H),
Alternatively, the content of the sum of hydrogen atoms (H) and halogen atoms (X) is preferably 1xlO" to 4xlO' atoms ppm. Furthermore, when the upper layer is composed of a polycrystalline material, Hydrogen atoms (H) contained in the upper layer,
Alternatively, the total content of hydrogen atoms (H) and halogen atoms (X) is preferably 1 x 103 to 2 x 10 s atoms ppm, and when composed of an amorphous material, The preferred range is 1 x 104 to 7 x 10' atoms ppm.

In the present invention, the upper layer composed of Non-3i (H, Law, HRCV D
The FoCVD method is preferable. These methods may be used in combination within the same device system.

For example, Non-3i (H
, X), basically a Si supply gas capable of supplying silicon atoms (St);
N supply gas capable of supplying hydrogen atoms (H) and/or X supply gas capable of supplying halogen atoms (X), and M capable of supplying atoms (M) controlling 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 n
) is introduced at a desired gas pressure into the activation space provided at the front stage of the deposition chamber, the interior of which can be reduced in pressure, separately or together as required. Active species (A) are generated by generating glow discharge or heating in the activation space, and hydrogen atoms (H
) and/or 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) are separately introduced into the deposition chamber, and N on S is placed on the surface of a support on which a predetermined lower layer is formed.
A layer consisting of i(H*X) may be formed.

To form the upper layer composed of Non-8t (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 supply gas that can supply tin atoms (S A gas is introduced into the deposition chamber at a desired gas pressure separately from the supply gas, and these gases are chemically reacted in the deposition chamber to form a predetermined lower layer that has been placed in a predetermined position in advance. A layer made of Non-8i (H,X) may be formed on the surface of the support.

In order to form the upper layer composed of Non-3i (H,
It may be formed by a known method described in Publication No. 2 and the like.

In the present invention, when forming the upper layer, atoms (M) that control conductivity contained in the layer, carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge
), the distribution concentration C of tin atoms (S n) (hereinafter collectively abbreviated as [atoms (MCNOGS) J) is changed in the layer thickness direction to obtain a desired distribution state in the layer thickness direction (dept
hprofile), in the case of the glow discharge method, HRCVD method, and FOCvD method, the source gas for supplying atoms (MCNOGS) whose distribution concentration is to be changed is changed by changing the gas flow to the desired change. 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.

A substance that can be used as the Si supply gas used in the present invention is SiH4,5t2Ha.

S 1 s Hs + S 14 H+. S t H
a and S 12 Ha are preferred. Further, these raw material gases for supplying Si may be diluted with gases such as Hz, He, Ar, Ne, etc., as necessary.

Effective halogen supply gases used in the present invention include a number of halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferred examples include halogen compounds that can be converted into

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, B r F, CIF, CIFs+
BrF5. BrF,,IF3.1F? +ICI, IB
Examples include interhalogen compounds such as r.

Specific examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include 5iFa and Six Fe.

Preferable examples include silicon halides such as S iC1a + S iB r a .

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:

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

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

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the halogen atom supply gas, but in addition, I-IF and HCI.

Hydrogen halides such as HBr and Hl, 5il-13F.

SiH2F2+ 5iHFa, 5iHz
I2. SiH2C12,5iHC1,
, 5iHa Br2 5iHBr, etc., and gaseous or gasifiable substances such as halogen-substituted silicon hydrides such as , 5iHa Br2 5iHBr, etc., can also be mentioned as effective raw materials for forming the upper layer. Among these substances, halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming the upper layer. In the present invention, it is used as a suitable halogen supply gas.

In order to structurally introduce hydrogen atoms into the upper layer, in addition to the above, HE or SiB4. S lx Ha.

Silicon hydride such as S i3 H,, Si4 I'Lo and S
This can also be carried out by causing discharge to occur by coexisting silicon or a silicon compound for supplying i in the deposition chamber.

To control the amount of hydrogen atoms (H) and/or halogen atoms (X) that may be contained in the upper layer, funae can be adjusted by adjusting the support temperature and/or the hydrogen atoms (H) or halogen atoms (X). What is necessary is to control the amount of the raw material used for inclusion into the deposition apparatus system, the discharge power, etc.

In order to structurally introduce atoms (M) that control conductivity into the upper layer, for example, group II atoms, group V atoms, or group II atoms, group A raw material for introduction, a raw material for introducing group V atoms, or a raw material for introducing group (III) atoms is placed in a gaseous state in a deposition chamber,
It may be introduced together with other raw materials for forming the upper layer. Materials that can be used as raw materials for introducing group (III) atoms or materials that can be used as raw materials for introducing group (III) atoms may be gaseous at normal temperature and pressure, It is desirable to use materials that can be easily gasified under the conditions.Specifically, B10.

B 4 H,, B, H,, B, H,
,,B,H,,,B.

Boron hydride such as H, , B, H, 4, BFL, BCI,
.

Examples include boron halides such as BBr.

In addition, AlCl3. GaCIa, Ga (CH3)5
．． InC15, TlCl3, etc. can also be mentioned.

In the present invention, the raw materials for introducing group (III) atoms that are effectively used for introducing phosphorus atoms include PH3,
North neighbor of hydrogen such as P and H4, PH4I.

PFs, PFs, PCl5, PCl5, PBr
s.

Examples include halogens such as PBr, Pl, etc. In addition, AsHs, AsF5, AsCI, +AsBr5
, AsFa , 5bHs , SbF3゜5bFs ,
SbCIs, SbCIa, B iHs.

B iC1s , B t B r s and the like can also be mentioned as effective starting materials for introducing Group V atoms.

Hydrogen sulfide (H2
S), SF, , SF,, SQ,, So□F2°CO3,C8,, CH, SH, C, H, SH.

C, H, S, (CH,), S, (C, H,
) 28 and the like. In addition, SeH2,5eFs, (CHI)
2Se, (C2Hs)2Se, T'eHz, Te
F'a.

Examples include substances in a gaseous state or which can be gasified, such as (CH3)2Te and (C2Hs)2Te.

In addition, H, He, etc. may be used as a raw material for introducing atoms (M) to control these conductivities, if necessary.

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

In order to structurally introduce carbon atoms (C), nitrogen atoms (N), or oxygen atoms (0) into the upper layer, a raw material for introducing carbon atoms (C) or nitrogen atoms must be used during layer formation. The raw material for introducing (N) or the raw material for introducing oxygen atoms (0) may be introduced in a gaseous state into the deposition chamber together with other raw materials for forming the upper layer. Raw material for introducing carbon atoms (C) or nitrogen atoms (N)
As 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 pressure, or that can be easily gasified at least 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.

Ru.

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C2Hll), propano (03Hs)
, n-butane (n Ca H+o) + pentane (C
,H,,), and the ethylene hydrocarbons include ethylene (
C2H4), propylene (C,H6).

Butene-1 (C,H,), Butene-2 (C4H8).

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

Acetylene (C2H2) is an acetylene hydrocarbon.
, methylacetylene (C1H,), butyne (C,H,'
) etc.

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

In addition to this, CF4. CCV,
, 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 (N2), which has N as a constituent atom, or has N and H as constituent atoms,
Ammonia (NH,).

hydrazine (H,NNH,), hydrogen azide (HN,),
Mention may be made of gaseous or gasifiable nitrogen such as ammonium azide (NH4N, ), nitrogen compounds such as nitrides and azides. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (F, N), nitrogen tetrafluoride (F4N
Examples include halogenated nitrogen compounds such as 2).

Starting materials that can be effectively used as raw material gases for introducing oxygen atoms (0) include, for example, oxygen (0,), ozone (03), and nitrogen oxide (No).

Nitrogen dioxide (N O2), -nitrogen dioxide (N20).

Nitrogen sesquioxide (N20.), trinitrogen tetraoxide (N.

04), nitrogen sesquioxide (N20s), nitrogen trioxide (NO
3) For example, disiloxane (I
3S its iHz), trisiloxane (H
Examples include lower siloxanes such as 3S its iHz O51H3).

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. Materials that can be used as raw materials for introducing germanium (Ge) or for introducing tin atoms (Sn) include materials that are gaseous at room temperature and pressure, or that can be easily gasified under layer-forming conditions. It is desirable that something be adopted.

As a material that can be a source gas for supplying Ge, GeH
4, Ge2Ha, GesHa, GeaHIo, G
es HI21 G es N141 G et H
Germanium hydride in a gaseous state or that can be gasified, such as 181 Ges Has, Gee I2°, is cited as one that can be effectively used, especially in terms of ease of handling during layer creation work, good Ge supply efficiency, etc. GeHa +
Preferable examples include Ge2Ha and GesHs.

In addition, GeHF5, GeI2F2. GeHsF,
GeHCIs T GeH2C,lz, GeH.

C1, GeHB r3 , GeH2B r2 , GeH
sBr, GeHIs, GeHa I2, Ge
Hydrogenated germanium halides such as Ha I, GeF,
.

GeCIa, GeBra, Ge I4. GeF2+
GeClx, GeBr2. Examples include germanium halides such as Ge 12.

As a substance that can be a source gas for supplying Sn, 5nH
a , 5n2Ha , Sns Hs , 5n4HLot
S ns N121 S n 6 H,,,S
n, Ho5tSns HISTSns
Gaseous or gasifiable tin hydride such as Hao+ can be effectively used, especially Sn Ha+3n, H due to its ease of handling during layer formation work and good Sn supply efficiency. , , Sns H, , are listed as preferred.

In addition, 5nHFs, 5nHz F! ,5nHsF
, 5nHC13, 5nHz Clz, 5nH3CI,
5nHBrs, 5nHaBr=, SnH*Br,
Hydrogenated tin halides such as 5nHIs, 5nHz 12 + SnH,I, 5nFa, SnC14.

5nBr, 5n14+ 5nFz, 5nC12°S
Gaseous or gasifiable substances such as tin halides such as nBr2, 5n12, etc. may also be mentioned as useful starting materials for forming the upper layer.

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

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

The gas pressure in the deposition chamber is appropriately selected in the optimum range according to the layer design, but in normal cases it is lXl0-'~10Torr,
Preferably 1xlO-' to 3T.

rr, optimally I X 10-' ~ I To r r
It is preferable that

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

The upper layer is Non-3i (H,X) and hydrogen atoms (H
) and/or polycrystalline silicon containing halogen atoms (X) (hereinafter abbreviated as rpoly-3i (H,X)J), various methods can be used to form 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, It is desirable to have a resistance of 5×10″ to LOW/c, preferably 5×10″ to 5W/crd, optimally 1×10″ to 2×10″W/crd.

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 rRF, +) glow discharge decomposition method.

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

1071・, 1072, 1073, 1074.1 in the diagram
075,1076.1077 gas cylinder and 107
The raw material gas for forming each layer of the present invention is sealed in the airtight container 8, 1071 is a SiH4 gas (purity 99.99%) cylinder, and 1072 is H gas (purity 99.9999%). %) cylinder, 1073 is S s F
a gas (99.99% purity) cylinder, 1074 is GeH
4 gas (purity 99.999%) cylinder, 1075 is H
82H diluted with 2 gases (purity 99°999%)
, hereinafter abbreviated as rB, H6/H2J), 1076 is N
o gas (purity 99.9%) cylinder, 1077 is He gas (purity 99.999%) cylinder, 1078 is AlCl3
It is a sealed container filled with (99.99% purity).

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

First, valves 1051 to 1077 of gas cylinders 1071 to 1077
1057, inflow valves 1031 to 1037, deposition chamber 10
After confirming that the leak valve 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, when the reading of the vacuum gauge 1017 becomes approximately lXl0-'Torr, the auxiliary valve 1018 and the outflow valve 1041
~1047 closed.

After that, SiH4 gas from gas cylinder 1071, H2 gas from gas cylinder 1072, and S from gas cylinder 1073.
iF, gas, G e Ha gas from gas cylinder 1074, BaHs/H2 gas from gas cylinder 1075, No gas from gas cylinder 1076, H from gas cylinder 1077
Introduce e-gas by opening valves 1051 to 1057,
Each gas pressure is adjusted to 2k by pressure regulators 1061 to 1067.
g/crrr.

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 rAlc) diluted with He gas
I3/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
．． 1043, 1046.1047 and auxiliary valve 10
18 gradually open S s Ha gas, H2 gas, 5I
F4 gas, No gas, and AlCls/He gas are introduced into the deposition chamber 1 through the gas discharge hole 1009 of the gas introduction pipe 1008.
001. At this time, the SiH4 gas flow rate was 50SCCM.

H2 gas flow rate is 10300M, No gas flow rate is 58CC
M, SiF, gas flow rate is 53 CCM.

Mass flow controllers 1021 and 1022 each so that the AlC1,/He gas flow rate is 1208 CCM.
, 1023, 1026.1027. Deposition chamber 1
The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the pressure inside the chamber 001 was 0.4 Torr. After that, the power of the RF power supply (not shown) was increased to 5 mW/cr.
rr and introduced RF power into the deposition chamber 1001 through the high frequency matching box 1012 to generate an RF glow discharge and initiate the formation of the lower layer on the cylindrical aluminum-based support. During the formation of the bottom layer, the SiH4 gas flow rate was 50SCCM, the SiF4 gas flow rate was 58CCM, and the N
o The gas flow rate is H2 so that it is a constant flow rate of 58CCM.
Mass flow controller 1021°10 so that the gas flow rate increases at a constant rate from 1105CC to 200SCCM, and the A I C1s/He gas flow rate decreases at a constant rate from 120SCCM to 40SCCM.
Adjust 22.1023, 1026.1027, layer thickness 0
．． Stop the RF glow discharge after forming the bottom layer of 0.05 μm, and also remove the outflow valves 1041, 1042, 104.
3,1046.1047 and the auxiliary valve 1018 are closed to stop the flow of gas into the deposition chamber 1001, the formation of the lower layer is completed, and the S i F 4 gas cylinder is replaced with a CH gas (purity 99.999%) cylinder. changed.

Next, to form the first layer region of the upper layer, the outflow valves 1041, 1042, 1044 and the auxiliary valve 10
Gradually open 18 and add 5iH4 gas, H2 gas, G e
Ha gas was introduced into the deposition chamber 10o1 through the gas discharge hole 1009 of the gas introduction pipe 1008. At this time, S i
Ha gas flow rate is 11005CC, H2 gas flow rate is ioo
Each mass flow controller 1021°102 so that sccM, GeH, and gas flow jl are 50SCCM.
Adjusted with 2.1024. The pressure inside the deposition chamber 1001 is
The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the pressure was 0.4 Torr. Thereafter, the power of the RF power source 1 (not shown) is set to 10 mW/crrr, and the power is supplied to the deposition chamber 100 through the high frequency matching box 1012.
Introducing RF power into 1 to generate an RF glow discharge,
Formation of the first layer region of the upper layer was started on the lower layer. During the formation of the first layer region of the upper layer, the SiH4 gas flow rate was 1
1005CC, H, gas flow rate is 0.5cc on the lower layer side so that the gas flow rate is a constant flow rate of 11005CC.
The mass flow controller 102 is set so that the flow rate is constant at 508 CCM at 7 μm, and decreases from 508 CCM to O3 CCM at a constant rate at 0.3 μm on the surface side.
1.1022°1024 was adjusted, and when the first layer region of the upper layer with a layer thickness of 1 μm was formed, the RF glow discharge was stopped, and the outflow valves 1041, 1042°1044 and the auxiliary valve 1018 were closed, and the deposition chamber was closed. The flow of gas into 1001 was stopped, and the formation of the first layer region of the upper layer was completed.

Next, to form the second layer region of the upper layer, the outflow valves 1041, 1042, 1045° 1046 and the auxiliary valve 1018 are gradually opened to supply SiH4 gas, H2 gas, B10. /H, gas, NO gas through gas inlet pipe 1008
The gas was allowed to flow into the deposition chamber 1001 through the gas discharge hole 1009 . At this time, the SiH4 gas flow rate is 100S1005
The mass flow controllers 1021, 1022, 1025, and 1026 were adjusted so that the CC gas flow rate was 11005 CC, B10°/I]2 gas flow rate was 800 ppm for SiH gas, and the No gas flow rate was IO8 CCM. While checking the vacuum gauge 1017, the main valve 10 is adjusted so that the pressure inside the deposition chamber 1001 is 0.4 Torr.
16 apertures were adjusted. Thereafter, the power of an RF power source (not shown) is set to 10 mW/crrr, and RF power is introduced into the deposition chamber 1001 through the high-frequency matching box 1012 to generate an RF glow discharge and cause the RF glow discharge to occur on the first layer region of the upper layer. Formation of the second layer region of the upper layer was started. During the formation of the second layer region of the upper layer, the SiH gas flow rate was ioos
ccM, H, gas flow rate is 11005CC, B10°/H
, so that the gas flow rate is constant at 800 ppm relative to S i H4 gas, and the No gas flow rate is a constant flow rate of IO8CCM at 2 μm on the bottom layer side, and decreases at a constant rate from IO8CCM to O8CCM at 1 μm on the surface side. mass flow controller 1021.1022,
1025° and 1026, and when the second layer region of the upper layer with a layer thickness of 3 μm was formed, the RF glow discharge was stopped.
In addition, the outflow valve 10111.1042゜1045.1
046 and the auxiliary valve 1018 to close the deposition chamber 10.
The flow of gas into 01 was stopped, and the formation of the second layer region of the upper layer was completed.

Next, to form the third layer region of the upper layer, the outflow valves 1041 and 1042 and the auxiliary valve 1018 are gradually opened to supply SiH4 gas and H2 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 SiHa gas flow rate is 3008CCM
, H, and gas flow rates were adjusted to 3008 CCM using mass flow controllers 1021 and 1022, respectively. The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the pressure inside the deposition chamber 1001 was 0.5 Torr. After that, the power of the RF power supply (not shown) is
5mW/err? High frequency matching box 1
Introducing RF power into the deposition chamber 1001 through 012,
RF glow discharge is generated, and the formation of the third layer region of the upper layer is started on the second layer region of the upper layer, and when the third layer region of the upper layer with a layer thickness of 20 μm is formed, the RF glow discharge is started. The flow of gas into the deposition chamber 1001 was stopped by closing the outflow valves 1041 and 1042 and the auxiliary valve 1018, thereby completing the formation of the third layer region of the upper layer.

Next, to form the fourth layer region of the upper layer, gradually open the outflow valves 1041, 1043 and the auxiliary valve 1018 to release the SiHa gas, CH.

Gas was flowed into the deposition chamber 1001 through the gas discharge hole 1009 of the gas introduction pipe 1008. At this time, SiH4
Gas flow rate is 503CCM, CH.

Each mass flow controller 1021 and 1023 was adjusted so that the gas flow rate was 5008 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 an RF power source (not shown) is
High frequency matching box 10 set to W/c rd
12 into the deposition chamber 1001, R
RF glow discharge was generated to start forming a fourth layer region on the third layer region of the upper layer, and when the fourth layer region of the upper layer with a layer thickness of 0.5 μm was formed, RF glow discharge was started. In addition, the outflow valves 1041 and 1043 and the auxiliary valve 1018 were closed to stop the gas from flowing into the deposition chamber 1001, and the formation of the fourth layer region of the upper layer was completed.

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

It goes without saying that the outflow valves for gases other than those necessary for forming each layer are completely closed, and each gas is not allowed to flow through the deposition chamber 1001 or the outflow valve 10.
In order to avoid remaining in the piping from 41 to 1047 to the deposition chamber 1001, the outflow valves 1041 to 104
7, open the auxiliary valve 1018, and then fully open the main valve to temporarily evacuate the system to a high vacuum, as necessary.

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

<Comparative example> H2 gas, No gas when forming the lower layer.

An electrophotographic light-receiving member was produced under the same production conditions as in Example 1, except that SiF4 gas was not used. Table 2 shows the conditions for producing this light-receiving member for electrophotography.

The electrophotographic light-receiving members of Example 1 and Comparative Example were set in an electrophotographic device that was a modified Canon NP-7550 copier for experimental purposes, and several tests were carried out under various conditions. When we checked the electrophotographic properties of both products, we found that they both have an excellent effect on preventing interference fringes on images, especially when long-wavelength light such as a semiconductor laser is used as the light source, and are characterized by the ability to obtain extremely high-quality images. It was found that it has.

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

In addition, in order to compare the degree of occurrence of image defects and layer peeling of the light-responsive layer due to relatively short-term impact mechanical pressure applied to the light-receiving member for electrophotography, a diameter of 3.5 m
Example 1: A stainless steel ball of 50 m was dropped freely from 30 cm vertically above the surface of the electrophotographic light receiving member and was applied to the surface of the electrophotographic light receiving member, and the probability of cracking in the light receiving layer was measured. It was found that the electrophotographic light-receiving member No. 1 had a probability of occurrence of 215 or less than the electrophotographic light-receiving member of 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> No gas was used in the lower layer, and AlC1s/
By changing the way the He gas flow rate changes, B,
An electrophotographic light-receiving member was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 3 by adding H,/H2N2 gas,
Similar evaluations were conducted, and as in Example 1, good effects were obtained in improving the edges, roughness, and layer peeling.

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

<Example 4> In the upper layer, H gas (not shown) was used as He gas (purity 99
．． 9999%), 5iFa gas, AlC1,/H
e Gas Gas N! A light-receiving member for electrophotography was prepared in the same manner as in Example 1 using gas (purity 99.999%) and under the preparation conditions shown in Table 5, and the same evaluation as in Example 1 was found. A good effect was obtained to improve the appearance of spots, roughness, and layer peeling.

<Example 5> In the upper layer, H gas was replaced with Ar gas (not shown) (purity 99
．． 9999%), CH4 gas was changed to NH gas (not shown) (purity 99.999%), SiFa gas was further used, and electrophotography was performed in the same manner as in Example 1 under the production conditions shown in Table 6. When a light-receiving member was prepared and evaluated in the same manner as in Example 1, it was found that, as in Example 1, good effects were obtained in terms of improvements in the areas of edges, roughness, and layer peeling.

<Example 6> CH gas was used instead of No gas in the lower layer of Example 1, and PH, /H2N2 (not shown) was used in the upper layer.
A light-receiving member for electrophotography was prepared in the same manner as in Example 1 using a gas concentration of 99.999%) and under the preparation conditions shown in Table 7, and the same evaluation was performed. A good effect was obtained in improving the appearance of spots, roughness, and layer peeling.

<Example 7> SiF4 gas and PH (not shown) in the upper layer.

An electrophotographic light-receiving member was prepared in the same manner as in Example 1 according to the preparation conditions shown in Table 8, further using /H, gas,
Similar evaluations were conducted, and as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 8> In the upper layer, PH, /H, gas (not shown).

An electrophotographic light-receiving member was produced in the same manner as in Example 1 using N2 gas and under the production conditions shown in Table 9, and was evaluated in the same manner as in Example 1. A good effect on layer peeling was obtained.

<Example 9> In the upper layer of Example 1, CH and gas cylinders were replaced with C and N2.
Instead of a gas (99.9999% purity) cylinder, use A.I.
An electrophotographic light-receiving member was produced in the same manner as in Example 1 using C1s/He gas and under the production conditions shown in Table 10, and the same evaluation was performed. A good effect of improving roughness and layer peeling was obtained.

<Example 10> In the upper layer, B2H gas was changed to PH3/H gas (not shown), SiF4 gas was further used, and light receiving for electrophotography was made in the same manner as in Example 1 under the production conditions shown in Table 11. When a member was prepared and evaluated in the same way, it was found that, similar to Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 11> In the upper layer, CH gas was replaced with NH gas (not shown), S n Ha gas (purity 99°999%) was further used, and the process was carried out under the production conditions shown in Table 12. An electrophotographic light-receiving member was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. As in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 12> Further using SiFa gas in the upper layer, the first
An electrophotographic light-receiving member was produced in the same manner as in Example 6 under the production conditions shown in Table 3, and the same evaluation was performed. As in Example 6, it was found to be improved against spots, roughness, and layer peeling. Good effects were obtained.

<Example 13> C2H, gas in the lower layer! 812 F 8 gas (
PH, /H2 gas (not shown) and S 12 Ha gas (purity 99.99%) were used in the upper layer.
99%) was used to prepare an electrophotographic light-receiving member in the same manner as in Example 9 under the preparation conditions shown in Table 14.
Similar evaluations were conducted, and as in Example 9, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 14> 312F6 gas was used in all layers, and P! (, /H2 gas was further used, and an electrophotographic light-receiving member was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 15, and the same evaluation was performed. A good effect was obtained in improving spots, roughness, and layer peeling.

<Example 15> An electrophotographic light-receiving member was prepared in the same manner as in Example 1 using GeH4 gas in the upper layer and under the preparation conditions shown in Table 16, and the same evaluation was conducted. Similar to No. 1, good effects were obtained in improving spots, roughness, and layer peeling.

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

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

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

<Example 19> In Example 1, the outer diameter of the cylindrical aluminum support was set to 15 mm, and a light-receiving member for electrophotography was prepared in the same manner as in Example 1 under 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 = 0.8
An electrophotographic light-receiving member was prepared using a cylindrical aluminum-based support having a diameter of μm under the same conditions as in Example 16.
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-based support was subsequently exposed to the dropping of numerous bearing applications, resulting in numerous droplets on the surface of the cylindrical aluminum-based support. A so-called surface dimple treatment that causes dents is applied, and the cross-sectional shape as shown in Fig. 39 is c=50μ.
Using a cylindrical aluminum support with m and d = 1 μm, an electrophotographic light-receiving member was produced under the same production conditions as in Example 16, and the same evaluation as in Example 16 was performed.
As in Example 16, good effects were obtained to improve the effects on creases, roughness, and layer peeling.

<Example 22> In Example 9, C and H2 gases were used instead of No gas, the temperature of the cylindrical aluminum support was 500°C, and the upper layer was made of pol according to the preparation conditions shown in Table 21.
An electrophotographic light-receiving member made of y-3i (H, Good effects were obtained.

<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 manufacturing apparatus for the RF glow discharge decomposition method shown in FIG. 37 is replaced with the deposition apparatus 71100 for the μW glow discharge decomposition method shown in FIG.
An apparatus for manufacturing electrophotographic light and receiving members using the μW glow discharge decomposition method shown in FIG.

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

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

Thereafter, in the same manner as in Example 1, each gas was introduced into mass flow controllers 1021 to 1027. However, in the upper layer, a CH gas cylinder was used instead of a No gas cylinder.

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

After the preparation for film formation was completed as described above, the lower layer and the upper layer were formed on the cylindrical aluminum support 1107. To form the bottom layer, drain valve 1
04'l, 1042°1043.1045,1046.
1047 and the auxiliary valve 1018 are gradually opened to
H, gas, H2 gas, and AIC1s/He gas were flowed into the plasma generation region 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, SiH
4 gas flow rate is 1508 CCMSH 2 gas flow rate is 20 SC
CM, SiF, gas flow rate is 10800M, No gas flow rate is IO3C0M, B, H.

/H, A ICI s / He gas flow rate is 40 so that the gas flow rate is tooppml for SiHa.
Each mass flow controller 1021.1022, 1023°1025.1026 so that 08CCM
．． Adjusted with 1027. The pressure inside the deposition chamber 1101 is 0.
．． The opening of the main valve (not shown) was adjusted so that the pressure was 6 mTorr while checking a vacuum gauge (not shown). Thereafter, the power of a μW power source (not shown) is set to 0.5 W/crrr, and μW power is introduced into the plasma generation region 1109 through the waveguide 1103 and the dielectric window 1102 to generate μW glow discharge, and the cylindrical aluminum Formation of the lower layer on the system support 1107 was started.

During the formation of the bottom layer, the SiHa gas flow rate was 1508CCM
, No gas flow rate is 10800M, B2H6 gas flow rate is S
1100pp for iH4.

S I F 4 gas flow rate is constant flow rate of 10800M, H2 gas flow rate is 20SCCM to 500SC
AlC1,/He increases at a constant rate in CM.
The mass flow controller 1 was set so that the gas flow rate decreased at a constant rate from 400 SCCM to 80 SCCM at 0.01 μm on the support side, and from 80 SCCM to 50 SCCM at 0.01 μm on the upper layer side.
021.1022,1023,1025°1026.1
027, and when a lower layer with a layer thickness of 0.02 μm was formed, the μW glow discharge was stopped, and the outflow valve 10
41,1042゜1043.1045.1046.10
47 and the auxiliary valve 1018 were closed to stop the flow of gas into the plasma generation region 1109, and the formation of the lower layer was completed. At this time, the No gas cylinder was changed to a CH gas cylinder.

Next, to form the first layer region of the upper layer, the outflow valves 1041, 1042, 1043° 1044, 1045
Then, the auxiliary valve 1018 is gradually opened to introduce SiHa gas, H gas, G e Ha gas, B2O, /H, gas, and SiF 4 gas into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. It flowed inside. At this time, the SiHa gas flow rate is 500, SCCM
,H.

Gas flow rate is 300 SCCMSGeH4 gas flow rate is 100
SCCM, B2O, /H, gas flow rate is 11000pp for SiH4 gas, SiF, gas flow rate is 203CCM
Each mass flow controller 1021
．． Adjusted at 1022°1023.1024.1025. The pressure inside the deposition chamber 1101 was adjusted to 0.4 mTorr. After that, the power of the μW power supply (not shown) is reduced to 0.
．． 5 W/crri to generate a μW glow discharge in the plasma generation chamber 1109 in the same way as the lower layer, to start forming the first layer region of the upper layer on the lower layer, and to form the first layer region of the upper layer with a layer thickness of 1 μm. A first layer region was formed.

Next, to form the second layer region of the upper layer, the outflow valves 1041, 1042, 1043° 1045 and the auxiliary valve 1018 are gradually opened to release S i H4 gas, H2
Gas, B2O, /H2 gas, and SiFa gas were flowed into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, the SiH4 gas flow rate is 500SCCM, and the H2 gas flow rate is 300SCCM.
MSB, H, /H, each mass flow controller 1021.
Adjusted with 1022, 1023, and 1025. Deposition chamber 11
The pressure inside 01 was adjusted to 0.4 mTorr. After that, the power of the μW power supply (not shown) was increased to 0.5W/cr.
rf and similar to the lower layer, the plasma generation chamber 1109
A μW glow discharge is generated within the layer, and the formation of the second layer region of the upper layer is started on the first layer region of the upper layer, and the layer thickness is 3 μm.
A second layer region of the upper layer was formed.

Next, to form the third layer region of the upper layer, the outflow valves 1041, 1042, 1043 and the auxiliary valve 10
Gradually open 18 and add SiHa gas, H2 gas, 5tF.
4 gases were flowed into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, the SiH4 gas flow rate is 7008CCM, the H2 gas flow rate is 500SCCM, and the SiFa gas flow rate is 303CC.
Each mass flow controller 102
Adjusted with 1.1022.1023. The pressure inside the deposition chamber 1101 was adjusted to 0.5 mTorr. Thereafter, the power of a μW power supply (not shown) is set to 0.5 W/c-, and μW
A glow discharge was generated and the formation of the third layer region of the upper layer was started on the second layer region of the upper layer, forming a third layer region of the upper layer with a layer thickness of 20 μm.

Then, to form the fourth layer region of the upper layer, gradually open the outflow valves 1041, 1046 and the auxiliary valve 1018 to release the SiHa gas, CH.

Gas was caused to flow into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time,
The mass flow controllers 1021 and 1026 were adjusted so that the S i Ha gas flow rate was 1508 CCM and the CH4 gas flow rate was 5008 CCM. Deposition chamber 11
The pressure inside 01 was 0.3 mTorr. Thereafter, the power of a μW power source (not shown) is set to 0.5 W/crrf to generate a μW glow discharge in the plasma generation region 1109, and the third layer region of the upper layer with a layer thickness of 1 μm is placed on the third layer region of the upper layer. Four layer regions were formed.

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

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

<Example 24> In Example 1, the CH4 gas cylinder was C and H.

A light-receiving member for electrophotography was prepared in the same manner as in Example 1 using a gas (purity 99.9999%) cylinder and under the preparation conditions shown in Table 23, and the same evaluation was performed as in Example 1. A good effect was obtained to improve the appearance of spots, roughness, and layer peeling.

<Example 25> SiFa gas was used in all layers, and B,
An electrophotographic light-receiving member was produced in the same manner as in Example 1, except that the H, /H, gas was replaced with a PH, /H, gas (not shown), and the same evaluation was conducted under the production conditions shown in Table 24. However,
As in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 26> In Example 1, the No gas cylinder was changed to an NH3 gas cylinder, CH gas was changed to NH gas in the upper layer, S n H4 gas (not shown) was further used, and the production conditions shown in Table 25 were performed. Accordingly, 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. Ta.

<Example 27> An electrophotographic light-receiving member was produced in the same manner as in Example 6 under the production conditions shown in Table 26, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 2...8> 812 Hs gas was further used in the upper layer, and the second
An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 7, and the same evaluation was performed. As in Example 1, it was found to be improved against spots, roughness, and layer peeling. Good effects were obtained.

<Example 29> PH, /H, gas is further used in the upper layer, and the second
An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 8, and the same evaluation was performed. As in Example 1, it was found to be improved in terms of edges, roughness, and layer peeling. Good effects were obtained.

<Example 30> The cylindrical aluminum support that was mirror-finished in Example 1 was subsequently exposed to the dropping of many bearing applications, resulting in countless dents on the surface of the cylindrical aluminum support. A so-called surface dimple treatment is applied, and the cross-sectional shape as shown in Fig. 39 is C=50μm5d=1μ.
Using a cylindrical aluminum-based support of m, in the upper layer, H gas was changed to He gas (not shown), and N gas (not shown) was
An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 29 using 2 gases, and the same evaluation was performed. A good effect of improving peeling was obtained.

<Example 31> An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 30, using A I C1s / He gas in the upper layer, and the same evaluation was performed. However, similar to Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 32> Electrophotographic light receiving was performed in the same manner as in Example 6 by further using AlC1,/He gas, No gas, and SIF a gas (not shown) in the upper layer, and under the production conditions shown in Table 31. When a member was prepared and evaluated in the same way, it was found that, similar to Example 6, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 33> The CH4 gas cylinder in Example 1 was changed to a C, H, gas cylinder, and an electrophotographic light-receiving member was manufactured in the same manner as in Example 1 under the manufacturing conditions shown in Table 32, and the same evaluation was conducted. As a result, similar to Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 34> In Example 1, CH and the gas cylinder were C2H.

Change to a gas cylinder and replace B, H, /H2 gas with PH (not shown)
, /H2 gas and under the production conditions shown in Table 33, an electrophotographic light-receiving member was produced in the same manner as in Example 1, and the same evaluation was performed. , a good effect on layer peeling was obtained.

<Example 35> In the upper layer, AlC1,/He gas, SiF4, H
An electrophotographic light-receiving member was prepared in the same manner as in Example 6 using a S/He (purity 99.999%) gas and under the preparation conditions shown in Table 34, and the same evaluation was performed. As in Example 6, good effects were obtained to improve the appearance of creases, roughness, and layer peeling.

<Example 36> C, H, and gases were further used from a cylinder not shown, and the third
A light-receiving member for electrophotography was produced in the same manner as in Example 9 under the production conditions shown in Table 5, and the same evaluation was conducted. As in Example 9, it was found to be good with improvements in spotting, roughness, and layer peeling. The effect was obtained.

<Example 37> A light-receiving member for electrophotography was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 36 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 38> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 37 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 39> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 38 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 40> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 39 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 41> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 40 and evaluated in the same manner. A good effect was obtained, which improved the results.

(Example 42) A light-receiving member for electrophotography was produced in the same manner as in Example 36 under the production conditions shown in Table 41 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 43> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 42 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 44> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 43 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 45>・PH and gas were further used from a cylinder not shown, and the 44th
A light-receiving member for electrophotography was produced in the same manner as in Example 36 under the production conditions shown in the table, and the same evaluation was performed. It worked.

<Example 46> An electrophotographic light-receiving member was prepared in the same manner as in Example 45 under the preparation conditions shown in Table 45 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 47> H2S gas was further used from a cylinder not shown, and the 46th
A light-receiving member for electrophotography was produced in the same manner as in Example 36 under the production conditions shown in the table, and the same evaluation was performed. It worked.

<Example 48> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 47 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 49> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 48 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 50> Using NH, gas, and I-128 gas from a cylinder not shown, Example 3 was prepared according to the preparation conditions shown in Table 49.
An electrophotographic light-receiving member was prepared in the same manner as in Example 6, and the same evaluation was performed. As in Example 36, good effects were obtained in improving spots, roughness, and layer peeling.

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

<Example 52> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 51 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 53> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 52 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 54> An electrophotographic light-receiving member was prepared in the same manner as in Example 45 under the preparation conditions shown in Table 53 and evaluated in the same manner. A good effect was obtained, which improved the results.

<Example 55> An electrophotographic light-receiving member was prepared in the same manner as in Example 36 under the preparation conditions shown in Table 54 and evaluated in the same manner. A good effect was obtained, which improved the results.

Table 1 Table 3 Table 4 Table 6 Table 7 Table 8 Table 9 Table 1 O Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 17 Table 18 Table 19 Table 22, Table 23, Table 24, Table 25, Table 26, Table 27, Table 28, Table 29, wtqn, Table 32, Table 33, It9i1 Ura 9 et al. 46 Front loading 4th Back side 48 m Loading 54 [Effects of the invention] By making the electrophotographic light-receiving member of the present invention have the specific layer structure as described above, the conventional electrophotographic light-receiving member made of A-3i It can solve all the problems in light-receiving materials, and in particular has extremely excellent electrical properties, optical properties,
Demonstrates 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 upper layer and the upper layer is improved, and the structural continuity of the constituent elements between the aluminum support and the upper layer is also improved, so roughness, spots, etc. It is possible to stably and repeatedly obtain high-quality images with improved image characteristics, clear 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 8i (H,
It can alleviate stress caused by differences in thermal expansion coefficients of i (H,X) films, prevent cracks and peeling of Non-8i (H,X) films, and improve productivity. .

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. Si),
Coupled with the effect of the distribution of hydrogen atoms (H), it is characterized by a remarkable improvement in image characteristics such as roughness and spots.

Furthermore, in the present invention, germanium atoms (Ge) and tin atoms (
By containing at least one of Sn), the adhesion between the upper layer and the lower layer is further improved, and the occurrence of image defects and peeling of the Non-8i (H,X) film is prevented. prevents this and improves durability. Furthermore, even if long-wavelength light such as a semiconductor laser is used as a light source for image exposure in an electrophotographic device, the long-wavelength light that cannot be completely absorbed between the surface side of the upper layer and the lower layer side is highly efficient. Therefore, the occurrence of interference phenomena due to reflection of long wavelength light at the interface between the upper layer and the lower layer and/or the surface of the support can be significantly prevented, and the image quality can be dramatically improved.

[Brief explanation of drawings]

FIG. 1 is a schematic block diagram for explaining the layer structure of a light-receiving member for electrophotography according to the present invention. FIG. 2 is a schematic block diagram for explaining the layer structure of a conventional light-receiving member for electrophotography. , Figures 3 to 8 respectively show aluminum atoms (AI), 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
Figures 17 to 36 are explanatory diagrams of the distribution states of atoms (NOc) and atoms (Mc) that adjust image quality, respectively, and atoms (M) that control conductivity and carbon atoms (C
) and/or nitrogen atoms (N) and/or oxygen atoms (0), germanium atoms (Ge) and/or tin atoms (S n), and FIG. FIG. 38 is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method using RF as an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography. FIG. 39 is an enlarged view of the cross section of the support when the cross-sectional shape of the aluminum support is V-shaped. FIG. 40 is a schematic illustration 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. 41A and 41B are schematic explanatory diagrams of a manufacturing apparatus using a glow discharge method using microwaves, which is an example of an apparatus for forming a light-receiving layer of a light-receiving member for electrophotography according to the present invention. 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 electrophotographic light-receiving member 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 101.8...Auxiliary valve 1020...Material gas supply device 1021-1027...Mass flow control 1031-1037 ...Gas inflow valve 1041-1
047...Gas outflow valve. 1051-1057... Valve 10 of raw material gas cylinder
61-1067...Pressure regulator 1071-1077...Material gas cylinder 1078...
・Hermetically sealed container for raw materials In FIGS. 40 and 41, 1100...deposition device 1101 using microwave glow discharge method...deposition chamber 1102...dielectric window 1103...waveguide section 1107... Cylindrical aluminum support 1109
...Plasma generation area 1010...Gas introduction pipe 1st I J Male/3 '1 120th 謬/, 4 [5 275th 2q '7 direction 2gth 30th day

Claims (1)

[Claims] (1) In a photoreceptive member having an aluminum-based support and a photoresponsive layer having a multilayer structure exhibiting photoconductivity on the support, the photoresponsive layer has at least aluminum atoms as a component from the support side. , silicon atom, hydrogen atom,
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; and an upper layer containing at least one of germanium atoms and tin atoms in a layer region in contact with the lower layer. A light-receiving member.