JPS63262658A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To enhance general characteristics by forming a photoreceptive member composed of a lower layer containing aluminum, silicon, and hydrogen each in a nonuniform distribution in the layer thickness direction, and an upper layer made of a nonmonocrystalline material containing silicon as a main component and at least one of hydrogen and halogen. CONSTITUTION:The photoreceptive member 102 is made of an inorganic material containing at least aluminum, silicon and hydrogen (AlSiH) as a constituent from the side of a support 101, and composed of the lower layer 103 having a part containing aluminum, silicon, and hydrogen each in a nonuniform distribution in the layer thickness direction, and an upper layer 104 made of a nonmonocrystalline material (Non-Si) containing silicon as a main component and at least one of hydrogen and halogen, thus permitting electric, optical, and photoconductive characteristics, durability, imaging characteristics, and characteristics of resistance to environmental conditions to be all enhanced.

Description

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

[Prior art]

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

Based on this point, amorphous silicon (hereinafter referred to as A-8i) is a photoconductive material that has recently attracted attention.
Application as a light-receiving member for electrophotography is described in JP 855718 and the like.

FIG. 2 is a cross-sectional view schematically showing the layer structure of a conventional electrophotographic light-receiving member, in which 201 is an aluminum support and 202 is a photosensitive layer made of A-8i. Such electrophotographic light-receiving members are generally produced by heating an aluminum-based support 20 to 50°C to 350°C, and depositing the aluminum on the support by vapor deposition, thermal CVD, plasma CVD, sputtering, etc. Photosensitive layer 20 made of A-8i by a film forming method
Create 2.

However, in this electrophotographic moonlight receiving member, since the thermal expansion coefficients of aluminum and A-8i are slightly different, cracks and peeling may occur in the A-8i sensitive light 202 during cooling after film formation, which poses a problem. It has become. 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-8
1. Stress caused by differences in thermal expansion coefficients of the photosensitive layers is alleviated, and cracks and peeling of the A-8i photosensitive layer are reduced.

[Problem that the invention seeks to solve]

However, the electrophotographic light-receiving member having a light-receiving layer composed of conventional A-3i has electrical, optical, photoconductive properties such as dark resistance value, photosensitivity, and photoresponsiveness, and usage environment characteristics. Individual improvements have been made in terms of stability, stability over time, and durability.
The reality is that there is room for further improvement in terms of improving overall characteristics.

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

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

Furthermore, when the electrophotographic light receiving member comes into contact with foreign matter that has entered the electrophotographic device, or when the electrophotographic light receiving member comes into contact with the electrophotographic device itself or maintenance tools during maintenance of the electrophotographic device, There have been problems 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-3i film, resulting in a reduction in productivity and yield.

Therefore, while efforts are being made to improve the properties of the A-8i 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 resolved. It is necessary to make improvements from this perspective.

[Means and effects for solving the problems] The electrophotographic light-receiving member of the present invention has an aluminum support and a multilayer light-receiving layer exhibiting photoconductivity on the support. In the light-receiving member, the light-receiving layer contains fewer co-aluminum atoms (
A1), silicon atoms (Si), and hydrogen atoms (H) (hereinafter abbreviated as rA1siH1), and the aluminum atoms (A1) and silicon atoms (S
i) and hydrogen atoms (I() in a non-uniform distribution in the layer thickness direction; and a lower layer containing silicon atoms (S
i) as a base material, and a non-single-crystalline material (rNon-8i (H.

(abbreviated as J)).

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

In particular, by containing aluminum atoms, silicon atoms, and especially hydrogen atoms in a non-uniform distribution in the layer thickness direction in the lower layer, the charge (photocarrier) between the aluminum-based support and the two-part layer can be reduced. ), and furthermore, the structural continuity of the constituent elements between the aluminum-based support and the upper layer is improved, so image characteristics such as roughness and spots are improved, and halftone It is possible to stably and repeatedly obtain high-quality images that appear clearly and have 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 Si (H,
i01. X) It is possible to alleviate the stress generated due to the difference in the coefficient of thermal expansion of the films, prevent cracks and peeling from occurring in the Non-3i (H, X) film, and improve the yield in terms of productivity.

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

[Detailed description of the invention]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic light-receiving member of the present invention will be described in detail below with reference to the drawings. FIG. 1 is a diagram schematically showing a preferred layer structure of the electrophotographic light-receiving member of the present invention.

The electrophotographic light-receiving member 100 shown in FIG. The lower layer 103 has a portion containing non-uniform distribution in the direction;
5i(H,X), and a photoreceptive layer 102 having a layered structure. Upper layer 104
has a free surface 105.

Aluminum-based support 101 used in the present invention
An aluminum alloy is used as the material. There are no particular limitations on the alloy components including the substrate aluminum in the aluminum alloy of the present invention, and the types, compositions, etc. of the components can be arbitrarily selected. Therefore, the aluminum alloy of the present invention has Japanese Industrial Standards (J
IS), AA standards, BS standards, DIN standards, international alloy registration, etc., for pure aluminum, Al-Cu, etc., which are standardized or registered as wrought materials, castings, die castings, etc.
Al-Mn series, Al-3i series, Al-Mg series, A1-M
Alloys with compositions such as g-3i series, Al-Zn-Mg series, etc.
l-Cu-Mg type (duralumin, super duralumin, etc.)
, A:1-Cu-3i system (Rautal etc.), Al-C
Contains u-Ni-Mg type (Y alloy, RR gold alloy), aluminum powder sintered body (SAP), etc.

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

Examples of pure aluminum include JISIloo,
Si and Fe 1.0% by weight or less, Cu O, 05-0
．． 20% by weight, In 0.05% by weight or less, Zn
O, 10% by weight or less, A1, 99.00% by weight or more.

As the Al-Cu-Mg system, for example, seal 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, MgO, 40-0.8% by weight, Zn
0.25% by weight or less, CrO, 10% by weight or less, A
1 The remainder is mentioned.

As the Al-Mn system, for example, JIS3003, Si
O, 6% by weight or less, FeO, 7% by weight or less, CuO
, 05-0.20% by weight, Mn 1.0-1.5% by weight
, Zn 0.40% by weight or less, and A1 balance.

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% by weight, Zn 0.25% by weight or less, CrO
, 10% by weight or less, NiO, 5-1.3% by weight, AI
The remainder is mentioned.

As the Al-Mg system, for example, JIS5086, Si
n, 40% by weight or less, Fe O, 50% by weight or less,
CuO, 10% by weight or less, MnO, 20-0.
7% by weight, Mg 3.5-4.5% by weight, Zn 0.
25% by weight or less, CrO, 05-0.25% by weight,
TiO, 15% by weight or less, balance A1.

1” Furthermore, Si 0.50% by weight or less, FeO,
25% by weight or less, CuO, 04-0.20% by weight,
Mn 0.01-1.0% by weight, MgO, 5-10
Weight%, 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 H2AI, and the balance A1.

Further, Si 0.12% by weight or less, Fed
, 15% by weight or less, Mn 0.30% by weight or less, M
g 0.5-5.5% by weight, ZnO, 01-1.0
Weight % or less, Cr O, 20 weight % or less, Zr O
, 01 to 0.25% by weight or less, and the remainder being AI.

As the Al-Mg-5i system, for example, JIS6063, SiO, 20 to 0.6% by weight, FeO, 35% by weight or less, Cub, 10% by weight or less, Mn 0.10
Weight% or less, Mg0.45-0.9% by weight, ZnO
, 10% by weight or less, Cr O, 10% by weight or less, Ti
Examples include O, 10% by weight or less, and the remainder A1.

As the Al-Zn-Mg system, for example, Seal 57NO1,
5iO0 30% by weight or less, Fe O, 35% by weight or less, Cu O, 20% by weight or less, Mn 0.20-0
．． 7% by weight, Mg 1.0-2.0% by weight, Zn 4.0
~5.0% by weight, CrO, 30% by weight or less, Ti
O, 20% by weight or less, Zr 0.25% by weight or less,
Vo, 10% by weight or less, balance A1.

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

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

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

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

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

That is, the surface of the support has irregularities smaller than the resolving power required for electrophotographic light-receiving members, and the irregularities are
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.

The lower layer in the present invention is composed of an inorganic material containing at least aluminum atoms (A1), silicon atoms (Si), and hydrogen atoms (I()) as constituent elements.

Aluminum atoms (A1), 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, their concentration is small in the layer thickness direction). There are parts where the distribution concentration is non-uniform.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

Further, in one of the preferred embodiments, aluminum atoms (AI), silicon atoms (
Si), the distribution state of hydrogen atoms (H) is such that aluminum atoms (Al), silicon atoms (Si), and hydrogen atoms (H) are continuously and uniformly distributed in the entire layer region, and The distribution concentration in the layer thickness direction decreases from the support side toward the upper layer, and silicon atoms (
Since the distribution concentration of hydrogen atoms (Si) and 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 (A1.) contained in the lower layer
The distribution state of silicon atoms (Si) and hydrogen atoms (H) is as described above in the layer thickness direction, and is uniformly distributed in the in-plane direction parallel to the surface of the support. is desirable.

3 to 8 show aluminum atoms (A1
) is shown as a typical example of the distribution state in the layer thickness direction.

In Figures 3 to 8, the horizontal axis is the aluminum atom (
The vertical axis indicates the layer thickness of the lower layer, t6 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 support side. The position of the end face of the lower layer is shown. That is, the lower layer containing atoms (A1) is formed from the tn side toward the tT side.

FIG. 3 shows a first typical example of the distribution state of atoms (A1) 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 (A1) is C81 from position 1B to position t31.
A distribution state is formed such that the concentration C81 decreases in a linear function from the position ts+ to the position t7, and reaches the concentration C32 at the position t7.

In the example shown in FIG. 4, the distribution concentration C of the contained atoms (A1) is from the position tB to the position tT.
The position t decreases linearly from 4□.

A distribution state is formed such that the concentration becomes C4□.

In the example shown in FIG. 5, the distribution concentration C of the contained atoms (A1) is the concentration C from the position t8 to the position t'r.
The concentration gradually and continuously decreases from 1 to 1, forming a distribution state in which the concentration reaches C62 at position ta.

In the example shown in FIG. 6, the distribution concentration C of the contained atoms (A1) is the concentration C6 from position tll to position t61.
A distribution state is formed in which the concentration takes a constant value of 1, decreases in a linear function from the concentration C62 from the position t61 to the position 1T, and reaches the concentration C113 at the position t'r.

In the example shown in FIG. 7, the distribution concentration C of the contained atoms (AI) takes a constant value of concentration C71 from position tn to position t71, and gradually increases from concentration C72 from position t71 to position tT. A distribution state is formed in which the concentration decreases continuously and reaches a concentration C73 at position t'r.

In the example shown in FIG. 8, the distribution concentration C of the contained atoms (AI) is the concentration CB+ from the position tn to the position tT.
A distribution state is formed in which the concentration gradually and continuously decreases from 1 to 2 to reach a concentration C8° at position t'r.

As described below with reference to FIGS. 3 to 8, some typical examples of the distribution state of atoms (A1) contained in the lower layer in the layer thickness direction, in the present invention, on the support side , contains silicon atoms and hydrogen atoms, and has a portion with a high distribution concentration C of atoms (A1), and has a portion where the distribution concentration C is considerably lower than that on the support side at the interface t. , a preferred example is formed. In this case, the maximum value Cmax of the distribution concentration of atoms (A1) is preferably 10 atomic % or more, more preferably 30 atomic % or more.
It is desirable that the layer be formed in such a manner that the distribution state is optimally 50 atomic % or more.

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

9 to 16 show typical examples of the distribution state of silicon atoms and hydrogen atoms contained in the lower layer of the electrophotographic light-receiving member of the present invention in the layer thickness direction.

In FIGS. 9 to 16, the horizontal axis represents silicon atoms (S
i) , hydrogen atom (H) (hereinafter collectively abbreviated as [atom (SH)J). However, silicon atom (S i)
and the distribution state of hydrogen atoms (H) in the layer thickness direction may be the same or different), the vertical axis indicates the layer thickness of the lower layer, and tll is the distribution state of the lower layer on the support side. ta indicates the position of the end face of the lower layer on the upper layer side. That is, the lower layer containing atoms (SH) is formed from the 1B side toward the tT side.

FIG. 9 shows a first typical example of the distribution state of atoms (SH) 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 (SH) is from position t to position t91.
The number increases from 91 to 1 hour, and the position t changes from the position tel.
A distribution state is formed that takes a constant value of concentration C9□ up to 'r.

In the example shown in FIG. 10, the distribution concentration C of the contained atoms (SH) increases linearly from the concentration C0°1 from the position t8 to the position tT, and at the position t'r the concentration CIO2 increases. The distribution state is formed as follows.

In the example shown in FIG. 11, the distribution concentration C of the contained atoms (SH) is from the position tB to the position t7.
From 111, the position t increases gradually and continuously. A distribution state is formed such that the concentration becomes CI+□.

In the example shown in FIG. 12, the distribution concentration C of the contained atoms (SH) increases numerically for one hour from the concentration C1□1 from the position t+l to the position t12°, and then increases from the concentration C1□1 to the position t12°. A distribution state is formed in which the concentration becomes CI2□, and the concentration takes a constant value of C123 from position t201 to position tT.

In the example shown in FIG. 13, the contained atoms (SH')
The distribution concentration C is at position 1. The concentration gradually increases continuously from C13 until reaching position t131, and then reaches position t, 3. The density becomes C132 at position t, 3. From position tT
Up to this point, a distribution state is formed in which the concentration takes a constant value of C533.

In the example shown in FIG. 14, the distribution concentration C of the contained atoms (SH) is from the position tB to the position tT.
A distribution state is formed in which the concentration increases gradually and continuously from 141 to reach a concentration C142 at position t.

In the example shown in FIG. 15, the atoms contained (S H)
The distribution concentration C is substantially zero from position t11 to position t151 (substantially zero here means the case where the amount is less than the detection limit, and the meaning of "substantially zero" hereinafter is also the same). ), the concentration C1, gradually increases at position t15,
1, and from position t16° to position t. Concentration C until seedlings
A distribution state is formed that takes a constant value of 152.

In the example shown in FIG. 16, the distribution concentration C of the contained atoms (SH) is at the position t1. From l to position tT, the concentration gradually increases from substantially zero until the concentration C1 increases at position tT.
61 is formed.

As described above with reference to FIGS. 9 to 16, some of the typical distribution states of atoms (SH) contained in the lower layer in the layer thickness direction, in the present invention, on the support side, aluminum Contains an atom (A1), and an atom (SH)
has a low distribution concentration C, and at the interface tT,
A preferable example is formed when the lower layer is provided with a distribution state of atoms (SH) having a portion where the distribution concentration C is considerably higher than that on the support side. In this case, the distribution state can be such that the maximum value Cmax of the distribution concentration of the sum of atoms (SH) is preferably 10 atomic % or more, more preferably 30 atomic % or more, and optimally 50 atomic % or more. It is desirable that the layers be formed like this.

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 at%, more preferably 10 to 90 at%,
The optimum content is preferably 20 to 80 atomic %.

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

In the present invention, the lower layer composed of A I S i H is formed by, for example, using the same vacuum deposition film forming method as the upper layer described later, and the numerical conditions of the film forming parameters are appropriately set so as to obtain the desired characteristics. and created. Specifically, for example, glow discharge method (low frequency CVD, high frequency CVD)
(AC discharge CVD such as D or microwave CVD, or DC discharge CVD, etc.), ECR-CVD method, sputtering method, vacuum evaporation method, ion blating method, optical CV
It can be formed by a number of thin film deposition methods such as the D method. These thin film deposition methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be produced. It is relatively easy to control the conditions for manufacturing electrophotographic light-receiving members with specific characteristics, and hydrogen atoms can be easily introduced in addition to aluminum atoms and silicon atoms. A discharge method, a sputtering method, and an ion blating method are suitable. These methods may be used in combination within the same device system. For example, by the glow discharge method,
To form the lower layer composed of A I S i H, basically A
1 raw material scrap for supply, Si supply gas capable of supplying silicon atoms (Si), and H capable of supplying hydrogen atoms (H).
A supply gas is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber, thereby depositing Al5ill on the surface of a predetermined support that has been placed in a predetermined position in advance. What is necessary is to form a layer consisting of.

When forming by sputtering method, for example, Ar,
A target made of A1 in an atmosphere of an inert gas such as He or a mixed gas based on these gases,
Hydrogen atoms (H
) is introduced into the deposition chamber for sputtering, and if necessary, a raw material gas for A1 supply and/or silicon atoms (Si) that can supply aluminum atoms (A1) is introduced into the deposition chamber for sputtering. This is accomplished by introducing a Si supplying gas capable of supplying Si into a deposition chamber for sputtering to form a plasma atmosphere of the desired gas.

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

In the present invention, when forming the lower layer, aluminum atoms (A1) and silicon atoms (Si) contained in the layer are
, hydrogen atom (H) (hereinafter these will be collectively referred to as "atom (A
A desired distribution state in the layer thickness direction (depth pro
In the case of the glow discharge method, in order to form a layer having a distribution of atoms (A S
H) This is accomplished by introducing the raw material gas for supply 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 (ASH) in a gaseous state, changing the gas flow rate appropriately according to a desired rate of change curve, and introducing the gas into the deposition chamber.

Second, the target for sputtering is, for example, A1
If a target containing a mixture of AI and Si is used, this can be done by changing the mixing ratio of AI and Si in advance in the layer thickness direction of the target.

Examples of substances that can be used as the raw material gas for supplying A1 used in the present invention include AlCl3. AIBra.

Al ■3. AI (CH,)2C1,AI (C
H, ),.

AI (OCH3),,AI (C,H5)3. AI
(OCI H6) 3, Al (i-C4H9)
! , AI (I C3H7)a, AI (CaI
2) s, AI(OC4H, )3, etc. can be cited as examples of those that can be effectively used. Further, these raw material gases for supplying A1 may be diluted with gases such as H, He, Ar, Ne, etc. as necessary.

Substances that can be used as raw material gas for supplying Si used in the present invention include SiH4 and Si2Ha.

Silicon hydride (silanes) in a gaseous state or that can be gasified, such as Si, H, , 5i4H, o, etc., can be cited as one that can be effectively used.
S'iH4,5i2Ha is preferred in terms of i supply efficiency. Further, these raw material gases for supplying Si may be diluted with gases such as H2, He, Ar, Ne, etc. as necessary.

Substances that can be used as raw material gas for hydrogen supply used in the present invention include H2+, 5iHa, 5i
Silicon hydrides (silanes) such as 2He, Sis Hs, and S14 HIO are effectively used.

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

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 the present invention, the end face of the lower layer with the aluminum support is a region where the content of aluminum atoms in the lower layer is 95% or less of the content of aluminum atoms in the aluminum support. This is because in a composition range in which the content of aluminum atoms exceeds 95% of the content of aluminum atoms in the aluminum-based support, its function is almost solely as a support. Furthermore, the end face of the lower layer with the upper layer is a region where the content of aluminum atoms in the lower layer exceeds 5%. This is because in a composition range where the content of aluminum atoms 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 formation guideline, but is usually in the range of lX10-' to 10 Torr, preferably IX10-' to 3 Torr.

The optimum value is preferably 1×10 −4 to ITorr.

The support temperature (Ts) is appropriately selected in an optimum range according to the layer formation needle, 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 AIS i H by the glow discharge method, the optimal range of discharge power supplied into the deposition chamber is selected as appropriate according to the layer formation guidelines, but in normal cases it is 5X10-5~ 10W/cpo, preferably 5X10-' to 5W/crrr.

Optimally l x 10"-" to 2 x 10-'W/
It is desirable to set it to cm8.

In the present invention, the above-mentioned desirable numerical ranges for the gas pressure in the deposition chamber, the support temperature, and the discharge power supplied to the deposition chamber for creating the lower layer include the above-mentioned ranges, but these layer creation factors are usually are not determined independently and separately, but it is desirable to determine the optimum value of the lower layer forming factor based on mutual and organic relationships in order to form a lower layer having desired properties.

QQ
- Upper "L layer" The upper layer in the present invention is Non-8i (H.

X) and has desired photoconductive properties.

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

There are a small number of atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge), and tin atoms (Sn) that control conductivity in the layer region of the upper layer. When one type of each is contained, 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 throughout the layer region, or may be evenly contained within the layer region, but depending on the layer thickness. There may be a portion containing the material in a non-uniformly distributed state with respect to the direction.

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

In addition, atoms (M) that control conductivity (hereinafter referred to as "atoms (M)"
(abbreviated as “layer region (M)”) (hereinafter referred to as “layer region (M)
) and a layer region (hereinafter referred to as "layer region") containing carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) (hereinafter abbreviated as "atoms (CNO)"). (abbreviated as “(CNO)”), germanium atom (abbreviated as
Ge) and/or tin atom (Sn) (hereinafter referred to as “atom (
The layer regions (hereinafter abbreviated as "layer regions (GS) J") containing the "layer regions (GS) They may be shared, or the respective layer regions may not be substantially shared.

17 to 36 show typical examples of the distribution state of atoms (M) contained in the layer region (M) in the layer thickness direction in the upper layer of the electrophotographic light-receiving member of the present invention. A typical example of the distribution state of atoms (CNO) contained in the layer region (CNO) in the layer thickness direction, atoms contained in the layer region (GS) (
GS) shows a typical example of the distribution state in the layer thickness direction.

(Hereafter, layer region (M), layer region (CNO), layer region (
GS) is represented by “layer region (Y)”, and atoms (M)
, Atom (CNO), Atom (GS)
Y)”. Therefore, FIGS. 17 to 36 show typical examples of the distribution state of atoms (Y) contained in the layer region (Y> in the layer thickness direction. (M), layer region (CNO), and layer region (GS) are substantially the same layer region, the layer region (Y) is included singularly in the upper layer, and is substantially the same layer region. If there is no layer region (Y), a plurality of layer regions (Y) are included 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 tIl
indicates the position of the end face of the layer region (Y) on the lower layer side, and tT indicates the position of the end face of the layer region (Y) on the free surface side. That is,
The layer region (Y) containing atoms (Y) is t from the tIl side.
A layer is formed toward the 7 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 the position tB to the position tT.
7, a distribution state is formed in which the concentration increases gradually and continuously to reach a concentration C172 at position tT.

In the example shown in FIG. 18, the distribution concentration C of the contained atoms (Y) is at the position t. From position t181, the concentration increases numerically from C181 for one hour, and at position t, 81, the concentration becomes CI8□, and from position t181 to position tT, a distribution state is formed in which the concentration takes a constant value of C183. There is.

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 t11 to position t191, and from position t19□ to position t192, the concentration C19, A distribution state is formed in which the concentration increases gradually and continuously from t1 to t2, and reaches a constant value of C093 from position t19° to position tT.

In the example shown in FIG. 20, the distribution concentration C of the contained atoms (Y) has a constant value of concentration C201 from position t11 to position t20+, and from position t201 to position t202. C202 is a constant value, and from position t202 to position t7 the concentration is C203.
A distribution state is formed that takes a certain value.

In the example shown in FIG. 21, the distribution concentration C of the contained atoms (Y) is C21 from position tll to position tT.
A distribution state is formed such that the value is a constant value.

In the example shown in FIG. 22, the distribution concentration C of the contained atoms (Y) is the concentration C2 from position tB to position t221.
2, and gradually and continuously decreases from the concentration C2□2 from position t2□1 to position tT, forming a distribution state in which the concentration reaches C223 at position t7.

In the example shown in FIG. 23, the distribution concentration C of the contained atoms (Y) is at the position t. Concentration C2 until position t1 is reached.
, 1 gradually and continuously decreases to form a distribution state such that the concentration becomes C2g□ at position tT.

In the example shown in FIG. 24, the distribution concentration C of the contained atoms (Y) is from position t11 to position t241.
241, and gradually and continuously decreases from the concentration C242 from the position t241 to the position tT, and at the position 1T, the distribution concentration C is substantially zero (here, substantially zero is the detection limit amount). (The meaning of "substantially zero" hereinafter is also the same).

In the example shown in FIG. 25, the distribution concentration C of the contained atoms (Y) is the concentration C2 from position 1B to position tA.
A distribution state is formed in which the distribution concentration C gradually and continuously decreases from 51 and becomes substantially zero at the position tT.

In the example shown in FIG. 26, the distribution concentration C of the contained atoms (Y) is from position t11 to position t261.
26, and decreases in a linear function from the concentration C261 from the position t261 to the position tT, forming a distribution state such that the concentration becomes C26□ at the position tA.

In the example shown in FIG. 27, the distribution concentration C of the contained atoms (Y) is the concentration C2 from position tB to position t7.
71, the distribution density C decreases in a linear function and forms a distribution state in which the distribution density C becomes substantially zero at the position tT.

In the example shown in FIG. 28, the distribution concentration C of the contained atoms (Y) is from position 1B to position t2B+.
Take a constant value of 281 and move from position t281 to position t'r
A distribution state is formed in which the concentration decreases in a linear function from the concentration C281 until reaching the concentration C282 at the position tT.

In the example shown in FIG. 29, the distribution concentration C of the contained atoms (Y) is from the position to to the positions t and r.
A distribution state is formed in which the concentration gradually and continuously decreases from 2.1 to reach a concentration C292 at position tT.

In the example shown in FIG. 30, the distribution concentration C of the contained atoms (Y) is from position t8 to position t3G+.
Takes a constant value of 301 and moves from position t301 to position tT.
The concentration decreases linearly from 0302 until the position t
A distribution state is formed such that the concentration becomes C303 at T.

In the example shown in FIG. 31, the distribution concentration C of the contained atoms (Y) increases gradually and continuously from the concentration C311 from the position tB to the position t311, reaches the concentration C812 at the position t311, and reaches the position C812. Position t7 from t3,1
Up to this point, a distribution state is formed in which the concentration takes a constant value of C3,3.

In the example shown in FIG. 32, the distribution concentration C of the contained atoms (Y) is the concentration C3 from position 1B to position t.
A distribution state is formed in which the concentration increases gradually and continuously from 21 to a concentration C322 at position tT.

In the example shown in FIG. 33, the distribution concentration C of the contained atoms (Y) is at position 1. The position 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 t331. At t331, the concentration becomes C83, and from position t33° to position tT, the concentration is C33.
A distribution state is formed that takes a constant value of 2.

In the example shown in FIG. 34, the distribution concentration C of the contained atoms (Y) is at position 1. The concentration C34 gradually increases from substantially zero until reaching position t'r.
, a distribution state is formed.

In the example shown in FIG. 35, the distribution concentration C of the contained atoms (Y) increases linearly from the concentration C351 from the position tB to the position t3,1, and increases from the concentration C351 to the position t35. A distribution state is formed in which the concentration takes a constant value C352 up to position tT.

In the example shown in FIG. 36, the distribution concentration C of the contained atoms (Y) is the concentration C36 from the position tl+ to the position t7.
, the concentration C increases at the position t.
362 is formed.

Examples of the atoms (M) that control the conductivity include so-called impurities in the semiconductor field. (abbreviated as "group atom") or n
Periodic table V excluding the nitrogen atom (N) which gives type conductivity properties
(hereinafter abbreviated as "Group V atoms") and oxygen atoms (0) (atoms belonging to Group Ⅰ of the periodic table (
Hereinafter abbreviated as "Group I atoms") will be used. Specific examples of the Group II atoms include B (boron), A1 (aluminum), Ga (gallium), In (indium), and TI (thallium), with B, AI, and Ga being particularly preferred.

Specifically, Group V atoms include P (phosphorus), As (arsenic), sb (antimony), and Bi (bismuth).
etc., with P and As being particularly suitable. Specifically, the Group Ⅰ atoms include S (sulfur), Se (selenium), Te
(tellurium), Po (polonium), etc., especially S, S
e is preferred. In the present invention, the atoms (M) controlling conductivity in the layer region (M) are group (III) atoms or group (III) atoms.
The inclusion of group atoms or group (III) atoms mainly has the effect of controlling the conductivity type and/or conductivity and/or the effect of controlling the conductivity type and/or the conductivity between the layer region (M) and the layer region other than the layer region (M) of the upper layer. The effect of improving charge injection properties can be obtained. The content of atoms (M) that control conductivity contained in the layer region (M) is preferably 1 x 10-3 ~
5X10' atomic ppm, more preferably 1X10-''~
lXl0' atoms ppm, optimally 1xio-' ~ 5X1
It is desirable that the level is 0” atomic ppm. Especially in the layer region (M
), the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) described later is l
When the content of atoms (M) that controls conductivity contained in the layer region (M) is preferably 1X10-3 to 1X103 atoms ppm, when the carbon atoms (C) and/or nitrogen atom (
N) and/or oxygen atom (○) content is 1×10
If it exceeds 3 atomic ppm, the atoms that control conductivity (
The content of M) is preferably 1 x 10-1 to 5 x 1
It is desirable that the amount is 0.04 atomic ppm.

In the present invention, carbon atoms (C) are added to the layer region (CNO).
and/or by containing nitrogen atoms (N) and/or oxygen atoms (0), mainly to increase the dark resistance and/or hardness and/or to control the spectral sensitivity and/or to control the layer region (CNO) and the upper part. The layer area of the layer (C
It is possible to obtain the effect of improving the adhesion between layer regions other than NO). The content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) contained in the layer region (CNO) is preferably 1 to 9X
105 atomic ppm, more preferably 1 x 101 to 5 x 1
06 atoms 1) I) m% optimally 1x102 to 3x105
Preferably, it is expressed in atomic ppm. In particular, when aiming for high dark resistance and/or high hardness, preferably 1 × 10
It is desirable that the concentration be 3 to 9 x 105 atomic ppm, and preferably 1 x 102 to 5X when controlling the spectral sensitivity.
Preferably, the amount is 10' atoms ppm.

In the present invention, by containing germanium atoms (Ge) and/or tin or atoms (Sn) in the layer region (GS), it is possible to mainly control the spectral sensitivity, and in particular, to use a semiconductor laser or the like as an image exposure source of an electrophotographic device. The effect of improving long wavelength light sensitivity when using long wavelength light can be obtained. Germanium atoms (
The content of Ge) and/or tin atoms (S n) is preferably 1 to 9.5 x 10 5 atomic ppm, more preferably 1 x 10 2 to 8 x 10 B atomic ppm.

The optimal amount is preferably 5 x 102 to 7 x 10' atoms ppm.

Further, hydrogen atoms (H) contained in the upper layer in the present invention
And/or halogen atoms (X) can compensate for dangling bonds of silicon atoms and improve layer quality. Hydrogen atoms (H) contained in the upper layer, or hydrogen atoms (
The total content of H) and halogen atoms (X) is preferably l
It is desirable that the content of halogen atoms (X) is from 1 to 4 x 1 atomic ppm.
It is desirable that the amount is 0.05 atomic ppm. In particular, the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) in the upper layer is 3X
In the case of 10' atomic ppm or less, the content of hydrogen atoms (H) or the sum of hydrogen atoms (H) and halogen atoms (X) is desirably 1 x 103 to 4 x 10' atomic ppm.

Furthermore, if the upper layer is composed of polycrystalline material,
The content of hydrogen atoms (H) or the sum of hydrogen atoms (H) and halogen atoms (X) contained in the upper layer is preferably 1XIO3 to 2X105 atomic ppm, and the amorphous If it is made of material, it is preferably l
It is desirable that Xl0' to 7 x 105 atomic ppm.

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

For example, to form an upper layer composed of Non-8i (H, N supply gas that can supply H) and/or X supply gas that can supply halogen atoms (X), M supply gas that can supply 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 Introducing a Ge supplying gas capable of supplying germanium atoms (Ge) and/or a Sn supplying gas capable of supplying tin atoms (Sn) at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, A glow discharge is generated in the deposition chamber, and N on S is deposited on the surface of a predetermined support that has been placed in a predetermined position and has a predetermined lower layer formed thereon.
1 (l(+X)).

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

To form the upper layer composed of Non-8i (H,
N supply gas capable of supplying H), M supply gas capable of supplying atoms (M) that control conductivity as necessary, and/or C supply gas capable of supplying carbon atoms (C), and /or N supply gas capable of supplying nitrogen atoms (N) and/or O supply gas capable of supplying oxygen atoms (0) and/or Ge supply gas capable of supplying germanium atoms (Ge) and/or Sn supply gas capable of supplying tin atoms (Sn) is introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, separately or together as required, and halogen (X) 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 consisting of Non-8i (H,X) may be formed on the surface of the support.

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

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

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

Substances that can be used as the Si supply gas used in the present invention include 5i) F4,512H6゜Sls Ha
* Silicon hydride (silanes) in a gaseous state or that can be gasified such as 8141 (10) is cited as one that can be effectively used, and it is also easy to handle during layer creation work, and has good Si supply efficiency. Preferred examples include S iH< and S 12H6.Furthermore, these raw material gases for supplying Si may be diluted with a gas such as H2, He, Ar, Ne, etc., as necessary.

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

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

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CIF, ClF31 BrF+z
BrF5. IF3, IF,, IC1
, IBr, and other interhalogen compounds.

Specifically, silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include, for example, 5IF4 + 812 F6.81C14, SiBr
Silicon halides such as No. 4 are preferred.

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

When forming an upper layer containing hydrogen atoms according to a glow discharge method or an HRCVD method, basically, silicon halide is used as a Si supply gas to form a layer on a desired support. Although the upper layer can be formed, in order to further facilitate the introduction of hydrogen atoms, a desired amount of hydrogen gas or gas of a silicon compound containing hydrogen atoms is also mixed with these residues. A layer may be formed.

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

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the halogen atom supply gas, but halogen compounds such as HF, HCI, HBr, and HI may also be used. , SiH3F, SiH2F2. SiHF3,5jH2I
2,5iH2C12,5iHC13,5iH2Br2,
Gaseous or gasifiable substances such as halogen-substituted silicon hydrides such as 5iHBrs can also be mentioned as effective raw materials for forming the upper layer. Among these substances, halides containing hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as halogen atoms are introduced into the layer when forming the upper layer. In the present invention, it is used as a suitable halogen supply gas.

In order to structurally introduce hydrogen atoms into the upper layer, in addition to the above, H2, SiHa, S12He, etc. can be used.

This can also be carried out by coexisting silicon hydride such as S 13 He or S 1.4 H+o with silicon or a silicon compound for supplying Si in the deposition chamber to generate discharge.

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

In order to structurally introduce atoms (M) that control conductivity into the upper layer, for example, group II atoms, group III atoms, or group III atoms, group A raw material for introduction or a raw material for introducing group Ⅰ atoms or a raw material for introducing group Ⅰ atoms is placed in a gaseous state in a deposition chamber.
It may be introduced together with other raw materials for forming the upper layer. Materials that can be used as a raw material for introducing group (III) atoms, a raw material for introducing group (III) atoms, or a raw material for introducing group (III) atoms are those that are gaseous at room temperature and pressure, or that are at least under layer-forming conditions. It is desirable to use a material that can be easily turned into dregs. Specifically, raw materials for introducing group (III) atoms include B2H6゜B4H1o, Bs H9, Bs I (+□
, Ba H+o, B6H,2, B6H,4, etc., BF3. Examples include boron halides such as BCl3°BBrs. In addition, AlCl2, GaC15,
Ga(cHs)s.

I n C] 3 , T I C1s, etc. may also be mentioned.

In the present invention, the raw materials for introducing group (IV) atoms that are effectively used for introducing phosphorus atoms are PH,
North neighbor of hydrogen such as P2H4, PH4I.

PF3, PF6, PCl5, PCl6. PBrs
.

PBr6. Examples include phosphorus halides such as PTs. In addition, A s Ha + A s F B + A s
CI 3+A s B r s + A s
F 5+ S b Ha , S b F s
+SbF5, SbC] 3, SbC]
□, B i Hs.

B i C] 3. B ], BBr a, etc. can also be mentioned as effective starting materials for introducing Group (I) atoms.

Hydrogen sulfide (H2
S) , SF, , SF, , Se, , SO2F.

CO8, C8,, CH3SH, C2H55H.

C4H4S, (CH3)25. Gaseous or gasifiable substances such as (C2H,)23 may be mentioned. In addition, SeH2,5eFa, (CH3)2]e, (C2H
6) 2Se, TaH2, TeFe.

(CH3) 2 Te, (C2IIS) 2 T
Examples include substances in a gaseous state or capable of being gasified, such as e.g.

In addition, raw materials for introducing atoms (M) to control these conductivities are H2, He, Ar, etc. as necessary.

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

To structurally introduce carbon atoms (C), nitrogen atoms (N), or oxygen atoms (0) into the upper layer, a raw material for introducing germanium (Ge) or a tin atom ( S n) The raw material for introduction may be introduced in a gaseous state into the deposition chamber together with other raw materials for forming the upper layer. Possible raw materials for introducing carbon atoms (C), nitrogen atoms (N), or oxygen atoms (0) include:
It is desirable to use a material that is gaseous at room temperature and pressure, or that can be easily gasified under layer-forming conditions.

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

Specifically, the saturated hydrocarbon is methane (CH,)
, ethane (C2H,), propane (C3Hs), n-butane (n C4I(+o), pentane (C5H,2
), ethylene hydrocarbons include engineered ethylene (C, H,
), propylene (C3H6).

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

Isobutylene (C4H,), pentene (C5H,,).

Acetylene (C2H2) is an acetylene hydrocarbon.
, methylacetylene (C3H4), butyne (C,H,)
etc.

As a raw material gas containing Sj, C, and H as constituent atoms, S
i (CH3)4. Mention may be made of alkyl silicides such as Si (C2H5)4.

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

Raw materials that can be effectively used as raw material gases for introducing nitrogen atoms (N) include nitrogen (N2), which has N as a constituent atom, or has N and H as constituent atoms,
Ammonia (NH3), hydrazine (H2NNH2),
Hydrogen azide (HNs).

Mention may be made of gaseous or gasifiable nitrogen such as ammonium azide (NH4N3), 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 (F3N), nitrogen tetrafluoride (F4N) can be introduced.
Examples include halogenated nitrogen compounds such as 2).

Starting materials that can be effectively used as raw material gas for introducing oxygen atoms (0) include, for example, oxygen (02),
tzo:/ (03), -nitric oxide (No).

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

Nitrogen sesquioxide (N203), trinitrogen tetraoxide (N204)
, nitrogen sesquioxide (N205), nitrogen trioxide (No2),
For example, disiloxane (H3) with silicon atom (S i), oxygen atom (0), hydrogen atom (H)
SiO8iHs)+ ) disiloxane (H3S iO
Examples include lower siloxanes such as 81H20S iHa ).

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

As a material that can be a source gas for supplying Ge, GeH
4, Ge2Ha, Ge3Hs, GeaHIon G
es NH21Ges N141 Ge7H16+Ge
8 H18, Ge9H20 and other germanium hydrides in a gaseous state or that can be gasified are effectively used, especially for ease of handling during layer creation work, Ge9H20, etc.
GeH4, Ge2H6, C8 in terms of supply efficiency, etc.
3H8 is preferred.

In addition, GeHBr5. GeH2F, GeHaF, G
eHCl3. GeH2C1□, GeHBr5. GeHB
r5, GeH2C1□, GeHsBr, GeHls
, GeHz I2, GeHg I, etc., hydrogenated germanium halides, GC! F4.

GeCIA, GeBra, GeI4, GeF2゜GeC1□, GeBr2. Examples include germanium halides such as GeI2.

Substances that can be used as raw material gas for Sn supply include SnH.
4, Snz H6, Sns HB, 5naH,, 5
n5H121Sna F141 8n,t F16゜S
Gaseous or gasifiable tin hydride such as nB H18+ S n and H201 can be effectively used, especially because of its ease of handling during layer formation work,
In terms of Sn supply efficiency, etc., Sn, H4゜5n2H
6, Sn, H, + are preferred.

In addition, SnH'F, 5nH2F2.5nHsF,
5nHC1s, 5nHz C1! z, 5nHsCC
5nHBra, '5nHz Br2, 5nHsBr,
Hydrogenated tin halides such as 5nHIs, 5nH2I2, 5nH3I, 5nF4, 5nCji! 4゜SnBr4
．． SnI4. SnF2,5nCj'2゜SnBr2+
Gaseous or gasifiable substances such as tin halides such as Sn 12 may also be mentioned as useful starting materials for forming the top layer.

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

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

The optimum range of gas pressure in the deposition chamber is selected according to the layer design, but normally it is lXl0-5 to 10 Torr.
, preferably I x 10-' to 3 Torr.

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

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

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

In the present invention, when the upper layer made of Non-8i (H, 5X10-' ~10W/c
m'', preferably from 5 x 10-' to 5 W/cm3, optimally from 1 x 10-3 to 2 x 10-'W/c to 3.

In the present invention, the above-mentioned desirable numerical ranges for the gas pressure in the deposition chamber, the support temperature, and the discharge power supplied to the deposition chamber for creating the upper layer include the above-mentioned ranges, but these layer creation factors are usually are not determined independently and separately, but it is desirable to determine the optimum value of the upper layer forming factor based on mutual and organic relationships in order to form an upper layer having desired properties.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

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

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 in the diagram; 1072, 1073, 1074.
1075, 1,076.1077 gas cylinders and 1
The raw material gas for forming each layer of the present invention is sealed in the airtight container 078, 1071 is a SiH4 gas (purity 99.99%) cylinder, and 1072 is a H2 gas (99.99% purity) cylinder.
1073 is a CH4 gas (purity 99°999%) cylinder, 1074 is a PH3 gas diluted with H2 gas (purity 99.999%, hereinafter referred to as "P").
1.075 is B diluted with H2 gas, H6 gas (purity 99°999%, hereinafter abbreviated as rB2H6/H2J), 1076 is N2 gas (purity 99.9999 %) cylinder, 1077 is He gas (purity 99.999%) cylinder, 1078 is AlC1
, (purity 99°99%).

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

First, valves 1051 to 1077 of gas cylinders 1071 to 1077
1057, inflow valve 1-031 to 1037, deposition chamber 1
After confirming that the leak valve 1015 of 001 is closed and that the outflow valves 1041 to 1047 and the auxiliary valve 1018 are open, first open the main valves 10 and 16 and turn on the vacuum pump (not shown). The deposition chamber 1001 and the gas piping were evacuated.

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

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

After that, SiH4 gas from gas cylinder 1071, H2 gas from gas cylinder 1072, and C from gas cylinder 1073.
H4 gas, PH3/H2 punishment from gas cylinder 1074,
B2H6/H2 gas from gas cylinder 1075, N2 gas from gas cylinder 1076, He from gas cylinder 1077
Gas is introduced by opening valves 1051 to 1057, and the pressure of each gas is adjusted to 2K by pressure regulators 1061 to 1067.
Adjusted to g/cm2.

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 the closed container 1078 filled with lCl3, AlCl3 gas (hereinafter rA]c diluted with He gas
]3/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
．． 1047 and auxiliary valve 1018 gradually open.
iH4 gas, H2 gas, AlC1, /He gas is introduced into the deposition chamber 1o through the gas discharge hole 1009 of the gas introduction pipe 1008.
was allowed to flow into the oi. At this time, the SiHa gas flow rate is 5
0SCCM, H2 gas flow rate is IO8CCM, AlCl3
/ Each mass flow controller 1021.1022.1027 so that the He gas flow rate is 1208 CCM.
Adjusted with. The pressure inside the deposition chamber 1001 is 0.4 Torr.
While checking the vacuum gauge 1017, the opening of the main valve 10J6 was adjusted so that the value was r. Thereafter, the power of an RF power source (not shown) is set to 5 mW/cm3, and RF is applied to the deposition chamber 1001 through the high frequency matching box 012.
Power was introduced to create an RF glow discharge and initiate the formation of the bottom layer on the cylindrical aluminum ram-based support.

During the formation of the bottom layer, the S I H4 gas flow rate was 503 CCM
The H2 gas flow rate was set at 1°SCCM so that the flow rate was constant.
A to increase at a constant rate from 200SCCM to 200SCCM.
lC1,/He gas flow rate is from 120SCCM to 40SC
Adjust the mass flow controllers 1021°1022.1027 so that the CM decreases at a constant rate, and the layer thickness is 0.
．． After forming the bottom layer of 0.05 μm, the RF glow discharge is stopped and the outflow valves 1041, 1042.104
7 and the auxiliary valve 1018 to close the deposition chamber 1001.
The flow of gas into the chamber was stopped, and the formation of the lower layer was completed.

Next, to form the first layer region of the upper layer, the outflow valves 104], 1.042 and the auxiliary valve 1018 are gradually opened to supply SiH4 gas and H2 gas to the gas inlet pipe 1.
008 into the deposition chamber 1001 through the gas discharge hole 1009. At this time, the 5jH4 gas flow rate is 3008C
Each mass flow controller 1021 and 1022 was used to adjust the CM and H2 gas flow rates to 3008 CCM. While checking the vacuum gauge 1017, adjust the pressure inside the deposition chamber 1001 to 0.5 Torr by turning the main valve 1016.
Adjusted the aperture. After that, the RF main power supply power (not shown) is set to 15 mW/cm3, and the high frequency matching box 1
Introducing RF power into the deposition chamber 1001 through 012,
RF glow discharge is generated, the formation of the first layer region of the upper layer is started on the lower layer, and when the first layer region of the upper layer with a layer thickness of 20 μm is formed, the RF glow discharge is stopped, and the outflow is started. Valve 1041, 10.42 and auxiliary valve 1
018 was closed to stop the flow of gas into the deposition chamber 1001, and the formation of the first layer region of the upper layer was completed.

Next, to form the second layer region of the two-part layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened to supply SiH4 gas and CH4 gas to the gas inlet pipe 10.
08 into the deposition chamber 1001 through the gas discharge hole 1009. At this time, the SiH4 gas flow rate is 50SCC
Each mass flow controller 1021 and 1023 was adjusted so that the MXCH4 gas flow rate was 5008 CCM. While checking the vacuum gauge 1017, adjust the pressure in the deposition chamber 1001 to 0.4 Torr by turning the main valve 1016.
Adjusted the aperture. After that, the RF main power supply power (not shown) is set to 10 mW/cm3, and the high frequency matching box 1
Introducing RF power into the deposition chamber 1001 through 012,
RF glow discharge was generated to start forming a second layer region on the first layer region of the upper layer, and when the second layer region of the upper layer with a layer thickness of 0.5 μm was formed, the RF glow discharge was started. Also, the outflow valves 1041, 1043 and the auxiliary valve 1018 were shut off to stop the flow of gas into the deposition chamber 1001, and the formation of the second layer region of the upper layer was completed.

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.
41 to 1o47 remain in the piping leading to the deposition chamber 1001, the outflow valves 1041 to 1o4
7, open the auxiliary valve 1018, and then fully open the main valve to temporarily evacuate the system to a high vacuum, as necessary.

During layer formation, the cylindrical aluminum support 1°05 is rotated at a desired speed by a drive device (not shown) in order to ensure uniform layer formation.

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

The electrophotographic light-receiving members of Example 1 and Comparative Example were set in an electrophotographic device that was a modified Canon NP-7550 copier for experimental purposes, and several tests were carried out under various conditions. The electrophotographic properties were checked.

When comparing the number of spots as an image characteristic, it was found that
．． The electrophotographic light-receiving member of Example 1 was 3/3 of the number of spots of 1 mm or less than the electrophotographic light-receiving member of Comparative Example.
It turned out that the number of points was 4 or less. moreover,
In order to compare the degree of roughness, a diameter of 0.05 mm was used.
The image density was measured at 100 points with a circular area as one unit, and the variation in the image density was evaluated.The results showed that the electrophotographic light receiving member of Example 1 was better than the electrophotographic light receiving member of Comparative Example 2. It was found that the electrophotographic light-receiving member of Example 1 was superior to the electrophotographic light-receiving member of Comparative Example even by visual inspection.

In addition, in order to compare the degree of occurrence of image defects and layer peeling of the light-receiving layer due to relatively short-term impact mechanical pressure applied to light-receiving members for electrophotography, a diameter of 3.5 m was measured.
A stainless steel ball of 30 cm was dropped freely from 30 cm vertically above the surface of the electrophotographic light-receiving member and was applied to the surface of the electrophotographic light-receiving member to measure the probability of cracks occurring in the light-receiving layer. It was found that the electrophotographic light-receiving member had a probability of occurrence of 315 or less than the electrophotographic light-receiving member of the comparative example.

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

<Example 2> An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 3 by changing the way the AlC1,/He gas flow rate changed in the lower layer, 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 3> An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 4 without using CH4 gas in the upper layer of Example '1, 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 4> In Example 1, the PH3/H2 gas cylinder was replaced with He scum (
(purity 99.9999%) into a cylinder, B2H6/N2
Change the gas cylinder to a No gas (purity 99.9%) cylinder, change the N2 gas to He gas in the upper layer, further use No gas, N2 gas, A ] C], / He gas, as shown in Table 5. An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown, and the same evaluation was performed. As in Example 1, it was found that it had good effects in improving spots, roughness, and layer peeling. Obtained.

<Example 5> In Example 1, the PH3/H2 gas cylinder was replaced with Ar gas (
Change the N2 gas cylinder to a NH, gas (purity 99°999%) cylinder,
In the upper layer, N2 gas was changed to Ar gas, CH4 gas was changed to NH3 gas, and an electrophotographic light-receiving member was created in the same manner as in Example 1 under the creation conditions shown in Table 6, and the same evaluation was performed. However, similar to Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 6> An electrophotographic light-receiving member was prepared in the same manner as in Example 1 using PH3/I (2 gas) in the upper layer and under the preparation conditions shown in Table 7, and the same evaluation was performed. However, similar to Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 7> In Example 1, the N2 gas cylinder was replaced with SiF4 gas (
A light-receiving member for electrophotography was produced in the same manner as in Example 1, using B2 Ha /H2 and S I F4 gases in the upper layer instead of the (purity 99.999%) cylinder, and according to the production conditions shown in Table 8. When the film was prepared and evaluated in the same manner as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 8> PH3/H2 gas and N2 gas were further used in the two-part layer, and an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 9, and the same evaluation was carried out. As a result, similar to Example 1, a good effect was obtained in which spots, roughness, and layer peeling were improved.

<Example 9> In Example 1, the CH and gas cylinders were changed to C2H2 gas cylinders (purity 99.9999%), the N2 gas cylinders were changed to NO gas cylinders, and in the upper layer, CH4 gas was changed to C2H2 gas, and No gas was further 10th using
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 10> An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 11, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 11> In Example 1, the N2 gas cylinder was replaced with NH, gas (purity 9
9.999%) CH4 in the upper layer instead of the cylinder
An electrophotographic light-receiving member was produced in the same manner as in Example 1, changing the gas to NH3 gas and using the production conditions shown in Table 12.
Similar evaluations were conducted, and as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 12> Example 6 was performed by changing the N2 gas cylinder to a SiF a gas cylinder in Example 6, and further using SiF 4 gas in the upper layer, and under the production conditions shown in Table 13.
An electrophotographic light-receiving member was prepared in the same manner as in Example 6, and the same evaluation was performed. As in Example 6, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 13> An electrophotographic light-receiving member was prepared in the same manner as in Example 9 using B2H6/H2 gas in the upper layer and under the preparation conditions shown in Table 14, and the same evaluation was performed.
Similar to Example 9, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 14> Further using PH3/H2 gas in the upper layer, the first
An electrophotographic light-receiving member was produced in the same manner as in Example 11 under the production conditions shown in Table 5, and the same evaluation was performed.
Similar to Example 11, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 15> In Example 1, the N2 gas cylinder was replaced with G e Ha gas (
A light-receiving member for electrophotography was prepared in the same manner as in Example 1, using G e H4 gas in the upper layer instead of the cylinder (purity 99.999%), and according to the preparation conditions shown in Table 16. As a result of the evaluation, as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 16> In Example 1, the outer diameter of the cylindrical aluminum support was 80 m, and according to the production conditions shown in Table 17,
An electrophotographic light-receiving member was prepared in the same manner as in Example 1, and evaluation was conducted in the same manner as in Example 1, except that an electrophotographic device modified from a Canon NP-9030 copying machine was used for the experiment. As in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 17> In Example 1, the outer diameter of the cylindrical aluminum support was set to 60 mm, and an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 18. Evaluations were conducted in the same manner as in Example 1, except that an electrophotographic device modified from a copying machine NP-1502 was used for the experiment, and as in Example 1, the problems with spots, roughness, and layer peeling were improved. Good effects were obtained.

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

<Example 19> In Example 1, the outer diameter of the cylindrical aluminum support was set to 15 mm, and a light-receiving member for electrophotography was prepared in the same manner as in Example 1 according to the preparation conditions shown in Table 20. Evaluations were conducted in the same manner as in Example 1, except that an electrophotographic device prototyped in 1999 was used, and as in Example 1, good effects were obtained in improving the problems of poling, roughness, and peeling of shoes.

<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 laminate-based support having a diameter of μm under the same conditions as in Example 16, and the same evaluation as in Example 16 was conducted.
Similarly, good effects were obtained in improving spots, roughness, and layer peeling.

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

<Example 22> In Example 9, the temperature of the cylindrical aluminum support was 500°C, and the upper layer was made of poly y-3i (H,X) according to the production conditions shown in Table 21. A light-receiving member for use was prepared in the same manner as in Example 9 and evaluated in the same manner as in Example 9. As in Example 9, good effects were obtained in improving spots, roughness, and layer peeling.

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

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

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

First, as in Example 1, the inside of the deposition chamber 1101 and the gas pipes were evacuated until the pressure in the deposition chamber 1101 reached 5×10 −6 Torr.

Thereafter, in the same manner as in Example 1, each gas was introduced into mass flow controllers 1021 to 1027. However, an S IF 4 gas cylinder was used instead of the N2 gas cylinder.

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

After the preparation for film formation was completed as described above, the lower layer and the upper layer were formed on the cylindrical aluminum support 1107. To form the bottom layer, drain valve 1
041,1042.1047 and auxiliary valve 1018
Gradually open S ] Ha gas, H2 gas, AI
C1,/He gas was flowed into the plasma generation region 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110.

At this time, the SI Ha gas flow rate is 150SCCM.

The mass flow controllers 1021, 1022, and 1027 were used to adjust the H2 gas flow rate to 20SCCMXAICI3/He gas flow rate to 4008CCM. The opening of a main valve (not shown) was adjusted so that the pressure inside the deposition chamber 1101 was 0.6 mTorr while checking a vacuum gauge (not shown). After that, the power of the μW power supply (not shown) is reduced to 0.
The waveguide section 1103 and the dielectric window 1 are set to 5W/Cm3.
μW power was introduced into the plasma generation region 1109 through 102 to generate a μW glow discharge and start forming a lower layer on the cylindrical aluminum-based support 11071. During the formation of the bottom layer, the AlC
l3/He gas flow rate is 40 at 0.01 μm on the support side.
In order to decrease at a constant rate from 0SCCM to 80SCCM, from 808CCM to 50SCCM at 0.01μm on the upper layer side.
'Adjust mass flow controller 1021.1022.1027 to reduce SCCM at a constant rate;
After forming the lower layer with a layer thickness of 0.02 μm, the μW glow discharge is stopped, and the outflow valves 1041, 1042.
1047 and the auxiliary valve 1018 were closed to stop the flow of gas into the plasma generation region 1109, and the formation of the lower layer was completed.

Next, to form the first layer region of the upper layer, the outflow valves 1041, 1042, 104.6 and the auxiliary valve 1
Gradually open 018 and add SiH4 gas, H2 gas, S I
F4 was allowed to flow into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, 5j H4 gas flow rate is 700SCCM, H2 gas flow rate is 500SCCM, S iFa gas flow rate is 303
Each mass flow controller 10 to be CCM
21. .

Adjusted with 1022.1026. The pressure inside the deposition chamber 1101 was adjusted to 0.5 m and Torr. After that, the power of the μW power supply (not shown) was increased to 0.5W/cm
3, a μW glow discharge is generated in the plasma generation chamber 1109 in the same way as for the lower layer, and the formation of the first layer region of the upper layer is started on the lower layer. A first layer region was formed.

Next, to form the second layer region of the upper layer, the outflow valves 1041 and 1.043 and the auxiliary valve 1018 are gradually opened to introduce the S I Ha gas and the CH4 gas into the gas inlet pipe 1110 (not shown). It was made to flow into the plasma generation space 1109 through the discharge hole. At this time, the S ] Ha gas flow rate is 150SCCM.

CH, each mass flow controller 1021. so that the gas flow rate is 5008 CCM. ．． Adjusted with 1023. The pressure inside the deposition chamber 1101 was 0.3 mTorr. After that, the power of the μW power supply (not shown) was increased to 0.5W/cm3.
A μW glow discharge is generated in the plasma generation region 1109, and a layer thickness of 1 μm is formed on the first layer region of the two-part layer.
A second layer region of the upper layer was formed.

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

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

Table 1 Table 2 Table 3 Table 6 Table 7 Table 10 Table 11 Table 14 Table 15 Table 18 Table 19 Table 22 [Effects of the Invention] Light receiving member for electrophotography of the present invention By having the above-mentioned specific layer structure, it is possible to solve all the problems in the conventional electrophotographic light-receiving member made of A-8i, and in particular, it has extremely excellent electrical properties and optical properties. Characteristic,
Indicates photoconductive properties, image properties, durability and use environment properties.

In particular, in the present invention, by containing aluminum atoms, silicon atoms, and especially hydrogen atoms in a non-uniform distribution state in the layer thickness direction in the lower layer, electric charge (photo carrier)
In addition, the structural continuity of the constituent elements between the aluminum support and the upper layer is improved, so image characteristics such as roughness and spots are improved, and halftones are clearer. It is possible to stably and repeatedly obtain high-quality images with high resolution and high resolution.

Furthermore, image defects and non-contamination may occur due to relatively short-term impact mechanical pressure applied to electrophotographic light-receiving members.
It prevents the occurrence of peeling of the 3i (H,
It is possible to alleviate the stress generated due to the difference in the thermal expansion coefficient of the i(t(,X) film, prevent cracks and peeling of the Non-3i (H, can.

[Brief explanation of the drawing]

FIG. 1 is a schematic block diagram for explaining the layer structure of a light-receiving member for electrophotography according to the present invention. FIG. 2 is a schematic block diagram for explaining the layer structure of a conventional light-receiving member for electrophotography. , FIGS. 3 to 8 are explanatory diagrams of the distribution state of aluminum atoms (AI) contained in the lower layer, respectively, and FIGS. 9 to 16 are respectively explanatory diagrams of the distribution state of aluminum atoms (AI) contained in the lower layer. , an explanatory diagram of the distribution state of hydrogen atoms (H), and FIGS. 17 to 36 respectively show atoms (M), carbon atoms (C), and/or atoms that control conductivity contained in the upper layer.
or nitrogen atom (N) and/or oxygen atom (O),
Germanium atoms (Ge) and/or tin atoms (S
Fig. 37 is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method using RF, which is an example of an apparatus for forming the light-receiving layer of the electrophotographic light-receiving member of the present invention. , FIG. 38 is an enlarged view of the cross section of the aluminum support when the cross-sectional shape of the aluminum support is V-shaped when forming the electrophotographic light receiving member of the present invention, and FIG. 39 is an enlarged view of the cross section of the support for forming the electrophotographic light receiving member of the present invention FIG. 40 is an enlarged view of a cross section of the support when the surface of the aluminum support is subjected to a so-called dimple treatment when forming a light-receiving member. FIG. FIG. 41 is a schematic explanatory diagram of a deposition apparatus using a microwave glow discharge method for forming a light-receiving layer of a light-receiving member for electrophotography according to the present invention. FIG. 2 is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method. Regarding FIG. 1, 100...Light receiving member for electrophotography of the present invention 101...
・Aluminum support 102...Pre-receiving layer 103...Lower layer 104...Upper layer 105...Regarding the free surface in FIG. 2, 200...Conventional light-receiving member for electrophotography 201...・
Aluminum support 202...Photosensitive layer 203 made of A-8i...Free surface In Fig. 37, 1000...Deposition device 1001 by RF glow discharge decomposition method...Deposition chamber 1005...Cylindrical Aluminum support 1008・
... Gas inlet pipe] 009 ... Gas discharge hole 1, 012 ... High frequency matching box 1014.
... Heating heater 1015 ... Leak valve 1016 ... Main valve 1017 ... Vacuum gauge] 018 ... Auxiliary valve 1020 ... Raw material waste supply device 1021-1027 ... Mass flow controller 1031 ..."037. ...Gas inflow valve 1041-1
．． 047...Gas outflow valve 1051-1057...
- Valve 1061 to 1067 of raw material gas cylinder... Pressure regulator 1071 to 1077... Raw material gas cylinder 1078...
・Hermetically sealed container for raw materials In FIGS. 40 and 41, 1100... Deposition apparatus 1 using microwave glow discharge method] 01... Deposition chamber 1102... Dielectric window 1103... Waveguide section 1107.・Cylindrical aluminum support 1109・
...Plasma generation area 1010...Gas introduction pipe

Claims (1)

[Claims] (1) In a photoreceptive member having an aluminum-based support and a photoreceptive layer having a multilayer structure exhibiting photoconductivity on the support, the photoreception layer has at least aluminum atoms and silicon atoms as constituent elements from the support side. a lower layer composed of an inorganic material containing atoms and hydrogen atoms and having a portion containing the aluminum atoms, silicon atoms, and hydrogen atoms in a non-uniform distribution state in the layer thickness direction; A light-receiving member comprising an upper layer made of a non-single crystal material containing at least one of halogen atoms.