JPS63265248A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To obtain a photoreceptive member for electrophotography exhibiting extremely superior electrical, optical and photoconductive characteristics, image characteristics, durability and characteristics in service environment by providing a specified layered structure. CONSTITUTION:A photoreceptive layer 102 on an Al-based support 101 is composed of a lower layer 103 made of an inorg. material contg. at least Al, Si and H atoms. as constituents and having a part contg. Al, Si and H atoms. distributed ununiformly in the thickness direction and an upper layer 104 made of an Si-based non-single crystalline material contg. H and/or halogen (X) atoms. and further contg. atoms (M) which control the conductivity of the material in a layered region kept in contact with the lower layer 103. The resulting photoreceptive member exhibits extremely superior electrical, optical and photoconductive characteristics, durability and characteristics in service environment.

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-3i) is a photoconductive material that has recently attracted attention.
Application as a light-receiving member for electrophotography is described in JP 855718 and the like.

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

However, in this electrophotographic moonlight receiving member, since the thermal expansion coefficients of aluminum and A-8i are different by about one order of magnitude, cracks and peeling may occur in the A-3i bad light 202 when cooling after film formation, which is a problem. It becomes. In order to solve these problems, JP-A-59-28162 proposes an electrophotographic photoreceptor consisting of an aluminum-based support, an intermediate layer containing a small amount of aluminum, and an A-3i photoreceptor. The intermediate layer containing at least aluminum alleviates the stress caused by the difference in thermal expansion coefficient between the aluminum support and the A-8i photosensitive material.
A-3i Reduces cracks and peeling caused by bad exposure.

[Problem that the invention seeks to solve]

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

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

In particular, as a result of improved image resolution, there is a reduction in non-uniformity in fine areas of image density, commonly known as "roughness", and a reduction in image defects in the form of black or white spots, commonly known as "pots". In particular, there has been a need to reduce "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-3i film, cracks and peeling occur in the A-Si film, resulting in a reduction in productivity and yield.

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

[Means and effects for solving the problems] The electrophotographic light-receiving member of the present invention is an electrophotographic light-receiving member having an aluminum-based support and a light-receiving layer having a multilayer structure exhibiting at least photoconductivity on the support. In the light-receiving member, the light-receiving layer contains at least aluminum atoms (A1), silicon atoms (Si), and hydrogen atoms (
H) (hereinafter abbreviated as rA1siHj)
a lower layer comprising a portion containing the aluminum atoms (A1), silicon atoms (Si), and hydrogen atoms (11) in a non-uniform distribution state in the layer thickness direction; and a base layer containing silicon atoms (Si). and a non-single crystal material containing at least one of a hydrogen atom (H) and a halogen atom (X) (hereinafter referred to as rNon-3i()I,X)
J) and an upper layer containing atoms (M) for controlling conductivity in a layer region in contact with the lower layer.

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, and usage 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, charge (photocarriers) between the aluminum support and the upper layer can be reduced. Injectability is improved, and furthermore, the structural continuity of the constituent elements between the aluminum support and the upper layer is improved, so image characteristics such as roughness and edges are improved, and halftones become 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 can alleviate stress caused by differences in thermal expansion coefficients of i(H,X) films, prevent cracks and peeling of Non-5i(H,X) films, and improve productivity. .

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

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

[Detailed description of the invention]

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

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

The electrophotographic light receiving member 100 shown in FIG. 1 is made of Al5iH on an aluminum support 101 for electrophotographic light receiving members, and the aluminum atoms, silicon atoms, and hydrogen atoms are The lower layer 103 has a portion containing the material in a non-uniform distribution state in the layer thickness direction;
A photoreceptive layer 10 having a layer structure consisting of n-5i()I,
2. Top layer 104 has a free surface 105.

Aluminum support 101 used in the present invention
An aluminum alloy is used as the material. There are no particular limitations on the alloy components including the substrate aluminum in the aluminum alloy of the present invention, and the types, compositions, etc. of the components can be arbitrarily selected. Therefore, the aluminum alloy of the present invention has Japanese Industrial Standards (J
IS), 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-8i series, ^1-Mg series, Al-M
Alloys with compositions such as g-5i series, Al-Zn-Mg series, etc.
l-Cu-Mg type (duralumin, similar duralumin, etc.)
, Al-Cu-3i system (Rautal etc.), Al-Cu
-Ni-Mg system (Y alloy, RR gold alloy), aluminum powder sintered body (SAP), etc. are contained.

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

Examples of pure aluminum include JISIloo,
Si and Fe 1.0% by weight or less, Cu O, 05-0.
20% by weight, Mn 0.05% by weight or less, ZnO,1
0% by weight or less, and 99.00% by weight or more of Al.

As the Al-Cu-Mg system, for example, Sei 52017 (
7), Si 0.05-0.20% by weight, Fe 0.7% by weight or less, Cu 3.5-4.5% by weight, Mn O, 40-
1.0% by weight, Mg 0.40-0.8% by weight, Zn0
．． Examples include 25% by weight or less, 0.10% by weight or less of Cr, and the remainder of A1.

As the ^l-Mn system, for example, JIS3003, Si
O, 6% by weight or less, Fe 0.7% by weight or less, Cu O,
05-0.20% by weight, Mn 1.0-1.5% by weight,
Examples include 0.10% by weight of Zn or less and the balance of A1.

As the Al-5i system, for example, JIS4032 Si
11.0 to 13.5% by weight, Fe 1.0% by weight or less, C
uO, 50-1.3% by weight, MgO, 8-1.3% by weight, Zn 0.25% by weight or less, CrO, 10% by weight
Hereinafter, NiO, 5 to 1.3% by weight, and the remainder A1 may be mentioned.

Al-Mg based technology, e.g. JI350860) S
t O, 40% by weight or less, Fe 0.50% by weight or less, C
u O, 10% by weight or less, Mn 0.20-0.7% by weight, Mg 3.5-4.5% by weight, Zn 0.25% by weight
Below, CrO, 05-0.25% by weight, TiO, 15
% by weight or less, the remainder of A1 may be mentioned.

Furthermore, Si 0.50% by weight or less, FeO,25
Weight% or less, Cu O, 04-0.20% by weight, Mn
O, 01-1.0% by weight, Mg O, 5-10% by weight,
Zn O, 03 to 0.25% by weight or less, Cr O, 05
~0.50% by weight, Ti or TrO, 05-0.20% by weight, H, 1.0 cc or less per 100 grams of AI, the remainder A1.

Furthermore, Si 0.12% by weight or less, FeO,1
5% by weight or less, MnO, 30% by weight or less, MgO, 5
~5.5% by weight, ZnO, 01~1.0% by weight or less,
CrO, 20% by weight or less, ZrO, 01-0.25
% by weight or less, the remainder of A1 may be mentioned.

As the Al-Mg-5i system, for example, JIS6063, SiO, 20 to 0.6% by weight, FeO, 35% by weight
Below, Cub, 10% by weight or less, MnO, 10% by weight
Below, Mg 0.45 to 0.9% by weight, Zn 0.10% by weight or less, Cr 0.10% by weight or less, Ti 0.10% by weight
The remainder of A1 is listed below.

As the ^1-Zn-Mg system, for example, JIS7NO1, Si 0.30% by weight or less, Fe O, 35% by weight or less, Cu O, 20% by weight or less, Mn 0.20-0.7
Weight %, Mg1. O~2.0% by weight, Zn4. O~5.
0% by weight, CrO, 30% by weight or less, TiO, 20
Examples include % by weight or less, ZrO, 25% by weight or less, Vo, 10% by weight or less, and the remainder of A1.

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

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

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

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

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

That is, the surface of the support has irregularities smaller than the resolving power required for electrophotographic light-receiving members, and the irregularities are caused by a plurality of spherical trace depressions.

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

1 Ri1 The lower layer in the present invention has at least aluminum atoms, (AI) silicon atoms (S i ),
It is composed of an inorganic material containing hydrogen atoms (H).

Aluminum atoms (A1), silicon atoms (Si), and hydrogen atoms (H) contained in the lower layer are evenly contained in the entire layer area of the lower layer, but they are There are parts where the distribution density is non-uniform. However, in the in-plane direction parallel to the surface of the support, it is necessary that the content be uniformly distributed and evenly distributed in order to make the properties uniform in the in-plane direction.

Further, in one of the preferred embodiments, aluminum atoms (AI) and silicon atoms (S
i), the distribution state of hydrogen atoms (H) is aluminum atoms (AI), silicon atoms (Si), hydrogen atoms (
H) Aluminum atoms (
The distribution concentration of AI) in the layer thickness direction decreases from the support side toward the upper layer, and silicon atoms (Si)
, since the distribution concentration of hydrogen atoms (H) in the layer thickness direction increases from the support side toward the lower layer,
Excellent compatibility between the aluminum support and the lower layer and between the lower layer and the upper layer.

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

3 to 8 show aluminum atoms (AI) contained in the lower layer of the electrophotographic light receiving member of the present invention.
) 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, t indicates the position of the end surface of the lower layer on the support side, and 11 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 (AI) is t.

The layer is formed from the side toward the t7 side.

FIG. 3 shows a first typical example of the distribution state of atoms (AI) 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 (AI) takes a constant value of concentration C31 from position t to position t□, and from position ts1 to position t7 the concentration C11. A distribution state is formed in which the concentration decreases in a linear function from , and the concentration becomes C1 at the position ta.

In the example shown in FIG. 4, the distribution concentration C of the contained atoms (AI) is the concentration C4 from position t to position i.
Decrease linearly from 1 to position t? At the concentration C
42 is formed.

In the example shown in FIG. 5, the distribution concentration C of the contained atoms (AI) is the concentration C8 from the position t6 to the position at〒.
Gradually and continuously decreases from I to position t? A distribution state is formed such that the concentration becomes C1 at .

In the example shown in FIG. 6, the distribution concentration C of the contained atoms (AI) is from position t to position tel, which is the concentration C6,
A distribution state is formed in which the density decreases from the density C6 from the position t0 to the position t7 in an order-of-magnitude manner, and reaches the density C6 at the position ta.

In the example shown in FIG. 7, the distribution concentration C of the contained atoms (AI) is from position t to position 11+, where the concentration Ca+
A distribution state is formed in which the concentration Cys gradually and continuously decreases from the position 11+ to the position t7, and reaches the concentration Cps at the position t7.

In the example shown in FIG. 8, the distribution concentration C of the contained atoms (A1) is the concentration CI from position t6 to position 11.
A distribution state is formed in which the concentration gradually and continuously decreases from I to reach the concentration C0 at position t7.

As described above with reference to FIGS. 3 to 8, some typical examples of the distribution state of atoms (A1) contained in the lower layer in the layer thickness direction, in the present invention, on the support side,
Contains silicon atoms and hydrogen atoms, and has a portion with a high distribution concentration C of atoms (AI), and has a portion where the distribution concentration C is considerably lower than that on the support side at the interface 1T, A preferred example is formed, in which the maximum value Cmax of the distributed concentration of atoms (AI) is preferably 1
It is desirable that the layer be formed in such a manner that a distribution state can be achieved such that the content is 0 atomic % or more, more preferably 30 atomic % or more, and optimally 50 atomic % or more.

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

9 to 16 show 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 axes represent silicon atoms and hydrogen atoms (hereinafter these will be collectively abbreviated as "atoms (SH)J". However, the distribution state of silicon atoms and hydrogen atoms in the layer thickness direction is the same. The vertical axis indicates the layer thickness of the lower layer, t indicates the position of the end surface of the lower layer on the support side, and t7 indicates the position of the end surface of the lower layer on the upper layer side. The position of the end face is shown. In other words, the lower layer containing atoms (SH) is formed from the t side toward the t layer 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) increases numerically for one hour from the concentration CI+ from position tll to positions t and l, and from position to+ to position t7. forms a distribution state that takes a constant value of concentration C92.

In the example shown in Figure 10, the contained atom (-3H)
The distribution concentration C of is the concentration C1 from position t to position 11.
A distribution state is formed in which the concentration increases linearly from 1° to a concentration C1° at position tT.

In the example shown in FIG. 11, the distribution concentration C of the contained atoms (SH) is from position t to position tT.
A distribution state is formed in which the concentration increases gradually and continuously from 1,1 to reach a concentration C11 at position i.

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 until the position tlff+, and the concentration at the position t1,1. C122, position t,. Position tT from 8
Until then, a distribution state is formed that takes a constant value of concentration C17.

In the example shown in FIG. 13, the distribution concentration C of the contained atoms (SH) gradually and continuously increases from the concentration C11 from the position t8 to the position t4.1, and reaches the concentration C132 at the position j +s+. , from position t3,1 to position ta, a distribution state is formed in which the concentration CI31 is a constant value.

In the example shown in FIG. 14, the distribution concentration C of the contained atoms (SH) is from position t to position t7.
14, and gradually and continuously increases to form a concentration C142 at position tr.

In the example shown in FIG. 15, the distribution concentration C of the contained atoms (SH) is substantially zero from position t to position t1,1 (here, substantially zero means that the concentration is below the detection limit). (the meaning of "substantially zero" in regret is also the same) and gradually increases from position t15. At the concentration Cl1ll
Then, the place is fl! A distribution state is formed in which the concentration takes a constant value of C+a2 from ils+ to position t.

In the example shown in FIG. 16, the distribution concentration C of the contained atoms (SH) gradually increases from the position t to the position tT, and at the position 1, the concentration C1,1
The distribution state is formed as follows.

As described above with reference to FIGS. 9 to 16, some typical examples of the distribution state of atoms (SH) contained in the lower layer in the layer thickness direction, in the present invention, aluminum atoms are and the distribution concentration C of atoms (SH)
A preferred example is when the lower layer is provided with a distribution state of atoms (SH) in which the distribution concentration C is considerably higher than that on the support side at the interface 11. is formed. In this case, atoms (SH
) is preferably 10
atomic% or more, more preferably 30 atomic% or more, optimally 5 atomic% or more
It is desirable that the layer be formed in such a way that a distribution state of 0 atomic % or more can be achieved.

In the present invention, the content of silicon atoms contained in the lower layer is appropriately determined as desired so as to effectively achieve the object of the present invention, but is preferably 5 to 9.
It is desirable that the content be 5 atomic %, more preferably 10 to 90 atomic %, most preferably 20 to 80 atomic %.

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

In the present invention, the lower layer composed of Al5iH is formed, for example, by the same vacuum deposition film forming method as the upper layer described later, with numerical conditions of film forming parameters set appropriately so as to obtain desired characteristics. Ru. Specifically, for example, glow discharge method (alternating current discharge CVD such as low frequency CVD, high frequency CVD or microwave CVD, or direct current discharge CVD), ECR-CVD method, sputtering method, vacuum evaporation method, ion blating method, optical CVD method,
It can be formed by a number of thin film deposition methods such as. These thin film deposition methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be produced. It is relatively easy to control the conditions for manufacturing electrophotographic light-receiving members with specific characteristics, and hydrogen atoms can be easily introduced in addition to aluminum atoms and silicon atoms. A discharge method, a sputtering method, and an ion blating method are suitable. These methods may be used in combination within the same device system. For example, by glow discharge method, Al5
In order to form the lower layer composed of iH, basically, a raw material gas for supplying AI that can supply aluminum atoms (AI), a gas for supplying Si that can supply silicon atoms (Si), and hydrogen. H supply gas capable of supplying atoms (H),
A gas is introduced at a desired pressure into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the deposition chamber, and Al
A layer consisting of 5iH may be formed.

When forming by sputtering method, for example, Ar,
A target made of AI, S in an atmosphere of an inert gas such as He or a mixed gas based on these gases.
using a target configured with i or with AI and S
Hydrogen atoms (H) using a mixed target of i
A raw material gas for supplying H that can supply aluminum atoms (A1) is introduced into the deposition chamber for sputtering, and if necessary, a raw material gas for supplying AI that can supply aluminum atoms (A1) and/or
Alternatively, a Si supply gas capable of supplying silicon atoms (Si) may be introduced into a deposition chamber for sputtering to form a plasma atmosphere of a 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, the distribution concentration C of aluminum atoms, silicon atoms, and hydrogen atoms (hereinafter collectively abbreviated as "atoms (ASH)") contained in the layer is determined in the layer thickness direction. In order to form a layer having a desired depth profile by changing the distribution concentration, in the case of the glow discharge method, the raw material for supplying atoms (A S H) whose distribution concentration should be changed changing the gas flow rate appropriately according to a desired rate of change curve,
This is accomplished by introducing it into the deposition chamber.

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

When forming by sputtering method, atoms (A S
) In order to change the distribution concentration C of () in the layer thickness direction to form a layer having a desired depth profile in the layer thickness direction, first, the same method as in the glow discharge method is used. 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.

Substances that can be used as raw material gas for supplying AI used in the present invention include AlCl, AlBr, and AlBr.

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

Al (OCHj) , AI (Cs Hs )
s.

AI C0C2Hs') 3, Al (I C
4He)31Al(i-CaH2)1. AI (C3H?
)3°AI (QC4He)S etc. can be cited as effective examples. In addition, these raw material gases for AI supply are converted into H* + He + A r as necessary.
It may be used after being diluted with a gas such as +Ne.

Substances that can be used as the raw material gas for supplying Si used in the present invention include SiHa and Si2Hs.

Silicon hydride (silanes) in a gaseous state such as S is Ha + S 14 H+o or which can be gasified is cited as one that can be effectively used, and furthermore, it is easy to handle during layer creation work and has good Si supply efficiency. SiH4,S
ix Ha is preferred. In addition, these raw material gases for Si supply may be converted into H2, He, etc. as necessary.
, Ar, Ne, etc. may be used after diluting with gas.

Substances that can be used as raw material gas for hydrogen supply used in the present invention include H21, 5IH4, SixH
Silicon hydrides (silanes) such as a, SlxHm, and 514HIG are effectively used.

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

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

In the present invention, the end face of the lower layer with the aluminum support is a region where the content of aluminum atoms in the lower layer is 95% or less of the content of aluminum atoms in the aluminum support. This is because in a composition 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 optimum range of the gas pressure in the deposition chamber is appropriately selected according to the layer formation guideline, but in normal cases it is between 1X10-' and 10 Torr, preferably between IX10-' and 3 Torr.

Optimally, it is preferable to set lXl0-' to I Tor r.

The support temperature (Ts) is appropriately selected in an optimal range according to the shoe design, but is usually 50 to 600°C, preferably 1
It is desirable to set it as 00-400 degreeC.

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

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges for the gas pressure in the deposition chamber, the support temperature, and the discharge power supplied into the deposition chamber for creating the lower layer, but these layer creation factors are However, the optimal values of the underlayer creation factors are determined based on mutual and organic relationships, which are usually not determined independently and separately. desirable.

Top” 1st layer The upper layer in the present invention is N□yl-8i(H.

X) and has desired photoconductive properties.

In the present invention, at least the layer region of the upper layer in contact with the lower layer contains atoms (CM) that control conductivity, including carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms ( Ge) and tin atoms (S n) are substantially not contained. However, in other layer regions of the upper layer, atoms controlling conductivity (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), germanium atoms (Ge), tin atoms ( It may contain at least one of the following. Particularly in the layer region near the free surface side of the upper layer, carbon atoms (C), nitrogen atoms (
It is preferable to contain at least one of N) and oxygen atoms (0).

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

Atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (O), germanium atoms (Ge
), a tin atom (S n), an atom (M) controlling the conductivity, a carbon atom (C), a nitrogen atom (N), an oxygen atom (0), a germanium atom ( Ge), tin atoms (Sn) may be uniformly distributed throughout the layer region, or may be uniformly contained within the layer region but non-uniformly in the layer thickness direction. There may be a portion containing it in a distributed state. However, in any case, it is necessary that the content be uniformly distributed and evenly distributed in the in-plane direction parallel to the surface of the support, in order to make the properties uniform in the in-plane direction. .

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

In addition, a layer region containing atoms (M) other than the layer region (Ml) (hereinafter abbreviated as "layer region (M t) J", and a layer region (
M, ) and layer region (M7) are collectively abbreviated as "layer region (M)"), layer region (CNO), and layer region (GS), even if they are substantially the same layer region. Alternatively, at least a part of each layer area may be shared, or each layer area may not be substantially shared.

17 to 36 show typical examples of the distribution state of atoms (M) contained in the layer region (M) in the layer thickness direction in the upper layer of the electrophotographic light-receiving member of the present invention. A typical example of the distribution state of atoms (CNO) contained in the layer region (CNO) in the layer thickness direction, atoms contained in the layer region (GS) (
GS) shows a typical example of the distribution state in the layer thickness direction. (Hereinafter, the layer region (M), layer region (CNO), and layer region (GS) will be referred to as "layer region (Y)" and atoms (
M), atom (CNO), and atom (GS) are represented by "atom (Y)". Therefore, in FIGS. 17 to 36,
A typical example of the distribution state of the atoms (Y) contained in the layer region (Y) in the layer thickness direction is shown, but as mentioned above, the layer region (M), the layer region (CNO), the layer region If (GS) are substantially the same layer area, the layer area (Y) is contained in a single unit in the upper layer, and if they are not substantially the same layer area, the layer area (Y) is included in the upper layer. (Multiple teeth are chipped inside).

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 t8 is the end face of the layer region (Y) on the lower layer side. ta indicates the position of the end face of the layer region (Y) on the free surface side. That is, the layer region (Y) containing atoms (Y) is formed as a layer from the t side toward the tT side.

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

In the example shown in FIG. 17, the distribution concentration C of the contained atoms (Y) is the concentration C1 from position t8 to position t7.
, 1 gradually and continuously increases, forming a distribution state in which the concentration reaches C1° at position t7.

In the example shown in FIG. 18, the distribution concentration C of the contained atoms (Y) increases numerically for one hour from the concentration C, . C1117, and from position t1111 to position ta, a distribution state is formed in which the concentration is C18, a constant value.

In the example shown in FIG. 19, the distribution concentration C of the contained atoms (Y) has a constant value of concentration CIll from position t to position jl**, and from position t1,1 to position t19. The concentration increases gradually and continuously from C1,1 until reaching , and reaches the concentration C10 at position j 1111,
From position t19ff to position t, a distribution state is formed in which the concentration takes a constant value of C10.

In the example shown in FIG. 20, the distribution concentration C of the contained atoms (Y) is from position t to position ts. The concentration becomes a constant value C8° until it reaches 1, and from position t 2a1 to position t. , the density becomes a constant value C1° until it reaches position t. , from position 1. Until then, a distribution state is formed in which the concentration takes a constant value of C1°.

In the example shown in FIG. 21, the distribution concentration C of the contained atoms (Y) is the concentration C3 from position 1ft11 to position tT.
A distribution state is formed that has a constant value of 1.

In the example shown in FIG. 22, the distribution concentration C of the contained atoms (Y) is at the position tI! The concentration is C up to position t221.
Takes a constant value of 2,1, and from position t2゜1 to position 11
The concentration gradually and continuously decreases from the concentration C23 until reaching the concentration C3 at the position t7.

The distribution state is formed as follows.

In the example shown in FIG. 23, the distribution concentration C of the contained atoms (Y) is C,
, 1, and gradually and continuously decreases to form a concentration C1, 2 at position t1.

In the example shown in FIG. 24, the distribution concentration C of the contained atoms (Y) is from the position tIl to the position t, the concentration C2 up to 4 degrees.
41, and gradually and continuously decreases from the concentration C24 from position t24° to position 11, and at position 11, the distribution concentration C becomes substantially zero (here, substantially zero does not mean substantially zero). In the case where the amount is less than the detection limit, a distribution state is formed such that the meaning of "substantially zero J" hereinafter is also the same.

In the example shown in FIG. 25, the distribution concentration C of the contained atoms (Y) is the concentration CI from position t8 to position tT.
A distribution state is formed in which the distribution concentration C gradually and continuously decreases from S'l to become substantially zero at position 11.

In the example shown in FIG. 26, the distribution concentration C of the contained atoms (Y) is from position tI+ to position t, and up to 61 is the concentration C3.
Take a constant value of 61, and from position t゛, 6□ to position 11
A distribution state is formed in which the concentration decreases in a -order function from the concentration C36 until reaching the concentration C36, and reaches the concentration C262 at the position 11.

In the example shown in FIG. 27, the distribution concentration C of the contained atoms (Y) is from the position t to the concentration C3 up to the position t7.
, 1, forming a distribution state in which the distribution concentration C decreases linearly from 1 to substantially zero at position ta.

In the example shown in FIG. 28, the distribution concentration C of the contained atoms (Y) is from position t to position t3. .

The density takes a constant value C1 up to the point t2. .

A distribution state is formed in which the concentration decreases in a linear function from the concentration C2,I up to the position 11, and reaches the concentration C2, at the position tT.

In the example shown in FIG. 29, the distribution concentration C of the contained atoms (Y) is the concentration C0 from position t8 to position ta.
, gradually and continuously decreases, forming a distribution state in which the concentration becomes -C'1° at position t7.

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

The density takes a constant value of C8°8 up to the position t. 1 to position t7, the concentration decreases in a -order function, forming a distribution state in which the concentration reaches C3° at position t7.

In the example shown in FIG. 31, the distribution concentration C of the contained atoms (Y) increases gradually and continuously from the concentration Call until position t, 11, and reaches the concentration C31 at position t III. , and the position t, 1. From position 11
Until then, a distribution state is formed that takes a constant value of concentration C□.

In the example shown in FIG. 32, the distribution concentration C of the contained atoms (Y) is 0.5% from position t to position t7.
A distribution state is formed in which the concentration increases gradually and continuously from 21 to a concentration C1 at position ta.

In the example shown in FIG. 33, the distribution concentration C of the contained atoms (Y) gradually increases from substantially zero from position t to position tal+, and then reaches the concentration C at position t3,1.
ssl, position t, 3. The density is 033 up to position 11! A distribution state is formed that takes a certain value.

In the example shown in FIG. 34, the distribution concentration C of the contained atoms (Y) gradually increases from substantially zero from position t to position 11, and reaches a concentration C14 at position t7. It forms a distribution state.

In the example shown in FIG. 35, the distribution concentration C of the contained atoms (Y) increases linearly from the concentration C3,1 from position t to position t 3111, and increases from the concentration C3,1 to position t sg
From t to position t7, a distribution state is formed in which the concentration takes a constant value of CS6□.

In the example shown in FIG. 36, the distribution concentration C of the contained atoms (Y) is C3,1 from position tm to position 11.
The concentration C increases linearly from , and at position t7, the concentration C,
, , a distribution state 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
Atoms belonging to Group V (hereinafter abbreviated as "Group V atoms")
and atoms belonging to Group Ⅰ of the periodic table excluding oxygen atom (0) (hereinafter abbreviated as ``Group Ⅰ atoms'') are used.

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

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

There are Sb (antimony), Bi (bismuth), etc.
Particularly suitable are P and As. Specifically, the Group Ⅰ atoms include S (sulfur) and Se (selenium).

There are Te (tellurium), Po (polonium), etc., especially S
, Se are preferred. In the present invention, layer region (M)
By containing a Group Ⅰ atom, a Group V atom, or a Group Ⅰ atom as an atom (M) that controls conductivity, the effect of controlling the conductivity type and/or conductivity and/or the layer region (M ) and the lower layer, and/or the effect of selectively controlling or improving the charge injection property or charge injection blocking property between the layer region (M) and the layer region (M) of the upper layer. It is possible to obtain the effect of improving the charge injection property during the period. The content of atoms (M) that control conductivity contained in the layer region (M) is preferably 1X10-" to 5X10' atoms 1)]) m%, more preferably 1x10-2 to 1x1O' atoms. ppm, optimally between 1.times.10@-1 and 5.times.10" atoms ppm.

In particular, in the layer region (M), carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0
) is less than lXl0'' atomic ppm, the content of atoms (M) that control conductivity contained in the layer region (M) is preferably 1xlO-'' to 1xlO' atomic ppm. It is desirable that carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms, (O
) exceeds lXl0'' atomic ppm, the content of the atom (M) that controls conductivity is preferably 5 or 1 x 10-' to 5 x 10' atomic ppm. .

In the present invention J, carbon atoms (C
) and/or nitrogen atoms (N) and/or oxygen atoms (0), mainly to increase dark resistance and/or hardness and/or to control spectral sensitivity and/or to control the layer region (CNO). The layer area of the upper layer (
It is possible to obtain the effect of improving the adhesion between layer regions other than CNO). The content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) contained in the layer region (CNO) is preferably 1 to 9.
X10' atoms ppm, more preferably lX10' to 5×
10S atoms ppm, optimally lXl0'~3X10'
Preferably, it is expressed in atomic ppm. In particular, when aiming for high dark resistance and/or high hardness, preferably lXl0
"~9X10'9X10'9 atoms is desirable, and when controlling the spectral sensitivity, preferably 1x10'~5X
Preferably, it is 10'' atomic ppm.

In the present invention, germanium atoms (
By containing Ge) and/or tin atoms (Sn), it is mainly used to control spectral sensitivity, especially to improve long wavelength light sensitivity when long wavelength light such as a semiconductor laser is used as an image exposure source in an electrophotographic device. You can get the effect of improving. Germanium atoms (Ge) contained in the layer region (GS)
) and/or the content of tin atoms (Sn) is preferably 1 to 9.5xlO' atomic ppm, more preferably 1x102 to 8x101' atomic ppm, optimally 5X
Preferably, it is between 10" and 7X10' atomic ppm.

Further, hydrogen atoms (H) contained in the upper layer in the present invention
And/or halogen atoms (X) can compensate for dangling bonds of silicon atoms and improve layer quality. Hydrogen atoms (H) contained in the upper layer, or hydrogen atoms (
The total content of H) and halogen atoms (X) is preferably l
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 0.06 atomic ppm. In particular, the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) in the upper layer is 3×
In the case of 101' atoms ppm or less, the content of hydrogen atoms (H) or the sum of hydrogen atoms (H) and norogen atoms (X) is desirably 1X10'' to 4X10'4X10' atoms 9. , when the upper layer is composed of a polycrystalline material, the content of hydrogen atoms (H) or the sum of hydrogen atoms (H) and halogen atoms (X) contained in the lower layer is preferably is desirably lXl0'' to 2x10' atomic ppm, and in the case of an amorphous material, it is preferably lXl0' to 7x106 atomic ppm.

In the present invention, the upper layer composed of Non-5i (H, Law, HRCVD
The FOCvD method is preferred. These methods may be used in combination within the same device system.

For example, in order to form an upper layer composed of Non-8i (H, ) and/or an X supply gas that can supply halogen atoms (X), and atoms (
M supply gas capable of supplying M) and/or C supply gas capable of supplying carbon atoms (C) and/or N supply gas capable of supplying nitrogen atoms (N) and/or oxygen atoms (0) 0 supply gas capable of supplying germanium atoms (G e) and/or Sn supply gas capable of supplying tin atoms (S n), the internal pressure of which can be reduced. A glow discharge is generated in the deposition chamber by introducing the gas under a desired pressure into the chamber, and the non-8T is deposited on the surface of a predetermined support, which has been placed in a predetermined position and has a predetermined lower layer formed thereon.
(H.

A layer consisting of X) may be formed.

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

To form the upper layer composed of Non-8i (H,
N supply gas capable of supplying H), M supply gas capable of supplying atoms (M) that control conductivity as necessary, and/or C supply gas capable of supplying carbon atoms (C), and /or N supply gas capable of supplying nitrogen atoms (N); and/or C supply gas capable of supplying oxygen atoms (0); and/or Ge supply gas capable of supplying germanium atoms (Ge); and/or 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-9i (H,X) may be formed on the surface of the support.

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

In the present invention, when forming the upper layer, atoms (M) that control conductivity contained in the layer, carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge
), the distribution concentration C of tin atoms (S n) (hereinafter collectively abbreviated as "atoms (MCNOGS) J") is changed in the layer thickness direction to obtain a desired distribution state (dept) in the layer thickness direction.
h profile), in the case of the glow discharge method, HRCVD method, and FOCVD method, the raw material gas for supplying atoms (MCNOGS) whose distribution concentration should be changed is changed by changing the gas flow rate as desired. This is accomplished by changing the rate appropriately according to the rate curve and introducing it into the deposition chamber.

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

Substances that can be used as the Si supply gas used in the present invention include SiH4,5i2Ha +Sii H+
,5i4JL. Silicon hydride (silanes) in a gaseous state or which can be gasified is cited as one that can be effectively used, and in addition, SiHa, S lz Ha is preferred. Further, these raw material gases for supplying Si may be diluted with gases such as H2, H, e, 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.

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

B,F,,B,F,,IF,,IF,,ICI.

Interhalogen compounds such as IBr can be mentioned.

Silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include specific examples such as S
iF4. Preferred examples include silicon halides such as Six Fa and 5iC14°SiBr4.

When a silicon compound containing such a halogen atom is used to form the characteristic electrophotographic light-receiving member of the present invention by a glow discharge method or an HRCVD method, silicon hydride gas is used as the Si supply gas. Even if not used, No n-3i (H,X
) can be formed.

When forming an upper layer containing halogen atoms according to the glow discharge method or HRCVD method, the upper layer is basically formed on a desired support by using silicon halide, which serves as the S1 supply gas. However, in order to further facilitate the introduction of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be further mixed with these gases to form a layer. It's okay.

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

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

Hydrogen halides such as HI, S iHs F r Si
HiF2, 5iHFs, 5iH2Iz, SiH*
C1t.

Gaseous or gasifiable substances such as halogen-substituted silicon hydrides such as 5tHC)s, 5iHiBrz, and 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, SiH4, Si*Ha, etc.

Six Hs, 5i4H+. This can also be carried out by causing a discharge by causing silicon hydride such as and silicon or a silicon compound for supplying Si to coexist in the deposition chamber.

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

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

B.H. ,Bg　H,,B,H,,,B,H,. .

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

Examples include boron halides such as B C1s + B B r s. In addition, A I C1s, G a C
1s +Ga (cHs)l, InC15, TlC
15 etc. may also be mentioned.

In the present invention, effective raw materials for introducing Group V atoms include PH,
Hydrogen north neighbor of P, H, etc., PH, I.

PFs, PFa, PCl,, PCl,, PBrs.

Examples include halogen ratios such as PBrs, Pl, etc. In addition, A s Hs, A s F s, A s
01s.

AsBrs, AsFa, 5bHs, 5bFa
*SbF,, 5bC1s, 5bC1,, BiHs +
B iC1s , B i B r s and the like can also be mentioned as effective starting materials for introducing Group V atoms.

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

So, F,, CO8, CS,, CH, SH.

C, H, SH, C, H, S, (CH,), S.

(C,H,), S, and other gaseous or gasifiable substances may be mentioned. In addition, S e Hz, S e F s
.

(CHs)z Se, (Cz Hs)2 Se, T
aH2゜TeFs, (CHs)I Te, (C
Mention may be made of gaseous or gasifiable substances such as z Hs )2Te.

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

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

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

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C,H,), propane (C.

Hs), n-butane (n-Ci HIQ), pentane (C,H,, ), and ethylene hydrocarbons include ethylene (C,H,) and propylene (C,H,).

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

Isobutylene (C4H,), pentene (C,H,.).

Examples of acetylene hydrocarbons include acetylene (C2H2
), methylacetylene (C,H,).

Examples include butyne (C, H, ) and the like.

As a raw material gas containing St, C, and H as constituent atoms, S
i (CHI)4. In addition, carbon atoms (C) can include alkyl silicides such as Si CC2H3)4.
In addition to the introduction of halogen atoms (X), halogenated carbon gases such as CF, CC1, CH, and CF can be mentioned.

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

Mention may be made of gaseous or gasifiable nitrogen such as ammonium azide (NH4Ns), nitrogen compounds such as nitrides and azides. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (F, N), nitrogen tetrafluoride (F4N
, ), etc. can be mentioned.

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

Nitrogen dioxide (No, ), -nitrogen dioxide (N,O).

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

04), nitrogen sesquioxide (N, O,), nitrogen dioxide (No.
, ), for example, disiloxane (H m
SiO3iH3) + Trisiloxane (Ha S t
Examples include lower siloxanes such as OS i Hz O8i Hl ).

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

As a material that can be a source gas for supplying Ge, GeH
a, Gez Hs + Gas Hs + Ge4H
lo+ Ges Hlffl Ges Ho4t Ge
y H181G e @ H+s+ G e @ H2
Germanium hydride in a gaseous state or that can be gasified, such as G
Preferable examples include e H4+Gez Hs and Ges H@.

In addition, GeHF5. GeHz Fz, GeHoF,
GeHCis, GeHz Clz, GeHs Cl
゜GeHBr5, GeHz Brz, GeH
s Br.

Germanium hydrogenated halides such as GeHIs, GeH, I2, GeHx I, G e Fa, G e
C1a.

GeBr4. Ge1. GeFt, GeC12°GeBr
Examples include germanium halides such as x and Ge It.

SnH is a substance that can be used as a raw material gas for supplying SN.
4,5n2Ha, Sns Hs, 5n4HIO+
S n@H121S n@HHar S n7
H1618n8 Ho5t 3n, H,. Sn hydride in a gaseous state or that can be gasified is effectively used, especially in terms of ease of handling during layer formation work and good Sn supply efficiency.
Preferred examples include nx Hs and S ns Ha.

In addition, 5nHFs, 5nHi F2.5nHsF,
5nHCi, 5nH2Ctz, 5nHs C1゜5n
HBr+, SnHo Brz, 5nHs Br
.

5nH1,,5nH2I2 + 5nHs T and other hydrogenated tin halides, S n Fa, S n Cl
a.

S n B r 41 S n I 41 S n F
z + S n Cl x +5nBr,,5n12
Gaseous or gasifiable substances such as tin halides and the like may also be mentioned as useful starting materials for forming the upper layer.

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

Non-3i having characteristics that achieve the purpose of the present invention
In order to form the upper layer consisting of (H,X), it is necessary to appropriately set the gas pressure in the deposition chamber and the temperature of the support as desired.

The optimum range of gas pressure in the deposition chamber is selected according to the layer design, but in normal cases it is lXl0-'~10Torr
, preferably lXl0-' 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-3i (H,X) and hydrogen atoms (H
) and/or halogen atoms (X) (hereinafter abbreviated as rpoly-8i(H,X)J), there are various methods for forming the layer. There are several methods, such as the following.

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

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

In the present invention, when the upper layer made of Non-3i (H, 5X 10-” ~10W/
cm", preferably 5x10-' to 5W/cm"
S@suitably lXl0-"~2X10-'W/c
It is preferable to set it as "m".

In the present invention, the above-mentioned desirable numerical ranges for the gas pressure in the deposition chamber, the support temperature, and the discharge power supplied to the deposition chamber for creating the upper layer include the above-mentioned ranges, but these layer creation factors are usually are not determined independently and separately, but 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 raw material gas supply device 1020 and a deposition device 100.
1 shows an apparatus for manufacturing an electrophotographic light-receiving member using an RF glow discharge decomposition method.

1071.1072.1073.1074.10 in the diagram
75,1076.1077 gas cylinder and 1078
The raw material gas for forming each layer of the present invention is sealed in the sealed container, and 1071 is SiHa gas (
1072 is a H, gas (purity 99.9999%) cylinder, 1073 is a CH4 gas (purity 99°999%) cylinder, 1074 is a PH gas diluted with H, gas (purity 99 .999%, hereinafter rPH
, /H2J) cylinder, 1075 is B, H, gas diluted with H, gas (purity 99.999%, hereinafter r
(abbreviated as B, H, /H, j), 1076 is N2 gas (
purity 99.9999%) cylinder, 1077 is He gas (
purity 99.999%) cylinder, 1078 is AlC1, (
It is a sealed container filled with 99.99% purity).

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

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

Next, the reading on the vacuum gauge 1017 is approximately I x 10-”Tor.
When the temperature reaches r, the auxiliary valve 1018 and the outflow valve 10 are closed.
41-1047 were closed.

After that, SiHa gas from gas cylinder 1071, N2 gas from gas cylinder 1072, CH, gas from gas cylinder 1073, PH, /H, gas from gas cylinder 1074, B, H, /H, gas from gas cylinder 1075, N, gas from gas cylinder 1076. , H from gas cylinder 1077
Introduce e-gas by opening valves 1051 to 1057,
Each gas pressure is set to 2K by pressure regulators 1061 to 1067.
g/c+m”.

Next, the inflow valves 1031 to 1037 are gradually opened to supply each of the above gases to the mass flow controllers 1021 to 1021.
It was introduced within the 27th. At this time, the mass flow controller 1027 receives the He gas from the gas cylinder 1077.
Since it passes through a closed container 1078 filled with lC1, AlC1 gas (hereinafter rA1c) diluted with He gas
1. /HeJ) is introduced.

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

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

To form the bottom layer, the outflow valves 1041°1042
．． 1047 and auxiliary valve 1018 gradually open.
i Ha gas, H gas, and AlC1,/He gas were flowed into the deposition chamber 1001 through the gas discharge hole 1009 of the gas introduction pipe 1008. At this time, the SiH4 gas flow rate was 5
08CCM.

The H and gas flow rates were adjusted using mass flow controllers 1021, 1022 and 1027 so that the IO3CCM and AlC1,/He gas flow rates were 1203CCM. The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the pressure inside the deposition chamber 1001 was 0.4 Torr. After that, the power of the RF power supply (not shown) was increased to 5 mW.
/cm” and set it to high frequency matching box 1012.
RF power was introduced into the deposition chamber 1001 through the deposition chamber 1001 to create an RF glow discharge and initiate the formation of the bottom layer on the cylindrical aluminum-based support.

During the formation of the bottom layer, the SiHa gas flow rate was a constant flow rate of 503CCM, the H gas flow rate was increased at a constant rate from 1105CCM to 200SCCM;
C1,/He gas flow rate is from 120SCCM to 40SCC
The mass flow controllers 1021, 1022, and 1027 are adjusted so that M decreases at a constant rate, and the layer thickness is 0.
After forming the lower layer of 0.05 μm, the RF glow discharge was stopped, and the outflow valves 1041, 1042° 1047
Then, the auxiliary valve 1018 was closed to stop the gas from flowing into the deposition chamber 1001, and the formation of the lower layer was completed.

Next, to form the first layer region of the upper layer, the outflow valves 1041, 1042, 1045 and the auxiliary valve 10
18 gradually open SiHa gas, H, gas, B, H
,/Gas discharge hole 100 of H2N2 gas introduction pipe 1008
9 into the deposition chamber 1o01. At this time, S
iH4 gas flow rate is 11005CC,, H, gas flow rate is 5
00SCCM, B2H, /H2 gas flow rate is S I Ha
The mass flow controllers 1021, 1022 and 1025 were used to adjust the concentration to 200 ppm relative to the gas. 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 power of the RF power source (not shown) is set to 8 mW/Cm'', and the high frequency matching box 10
10, RF power is introduced into the deposition chamber 1001,
RF glow discharge is generated, the formation of a first layer region of the upper layer is started on the lower layer, and the RF glow discharge is stopped when the first layer region of the upper layer having a layer thickness of 3 μm is formed;
The outflow valves 1041, 1042, 1045 and the auxiliary valve 1018 were 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 upper layer, the outflow valves 1041 and 1042 and the auxiliary valve 1018 are gradually opened to introduce 5IH4 gas and Hj gas into the gas inlet pipe 1008.
The gas was allowed to flow into the deposition chamber 1001 through the gas discharge hole 1009 . At this time, the SiH4 gas flow rate is 3008 CCMSH
Each mass flow controller 1021.10'22 was adjusted so that the two gas flow rates were 300 SCCM. The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the pressure inside the deposition chamber 1001 was 0.5 Torr. After that, the power of the RF power source (not shown) is
High frequency matching box 10 set to W/cm''
RF power is introduced into the deposition chamber 1001 through the RF
A glow discharge is generated, the formation of a second layer region of the upper layer is started on the lower layer, and when the second layer region of the upper layer with a layer thickness of 20 μm is formed, the RF glow discharge is stopped, and the outflow valve is 1041, 1042 and the auxiliary valve 1018 were closed to stop the flow of gas into the deposition chamber 1001, and the formation of the second layer region of the upper layer was completed.

Next, to form the third layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened to supply SiHa gas, CH, and gas to the gas inlet pipe 10.
08 into the deposition chamber 1001 through the gas discharge hole 1009. At this time, the SiH4 gas flow rate is 503CCM
, CH, and gas flow rates were adjusted to 5008 CCM using mass flow controllers 1021 and 1023, respectively. The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the pressure inside the deposition chamber 1001 was 0.4 Torr. After that, the power of the RF power source (not shown) was set to 10 mW/cm'', 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 third layer region on the second layer region of the upper layer, and when the third 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 closed to stop the gas from flowing into the deposition chamber 1001, and the formation of the third layer region of the upper layer was completed.

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

It goes without saying that the outflow valves for gases other than those necessary for forming each layer are completely closed;
Each gas enters the deposition chamber 1001 and the outflow valve 104.
In order to avoid remaining in the piping from 1 to 1047 to the deposition chamber 1001, the outflow valves 1041 to 1047
, close the auxiliary valve 1018, and then fully open the main valve to temporarily evacuate the system to a high vacuum, as necessary.

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

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

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

It was found that both of these light-receiving members for electrophotography have the characteristic of exhibiting extremely good charging ability, but when comparing the number of spots as an image characteristic, it was found that
It was found that the number of holes in the electrophotographic light-receiving member of Example 1 was 3/4 or less of the number of holes in the electrophotographic light-receiving member of Comparative Example. Furthermore, in order to compare the degree of roughness, image density was measured at 100 points with a circular area with a diameter of 0.05 mm as one unit, and the variation in image density was evaluated. The receiving member has a variation of 2/3 or less of the electrophotographic light-receiving member of the comparative example, and visually the electrophotographic light-receiving member of Example 1 is superior to the electrophotographic light-receiving member of the comparative example. I understand.

In addition, in order to compare the degree of occurrence of image defects and layer peeling of the light-receiving layer due to relatively short-term impact mechanical pressure applied to light-receiving members for electrophotography, a diameter of 3.5 m was measured.
A stainless steel ball of 30 cm was dropped freely from 30 cm vertically above the surface of the electrophotographic light-receiving member and was applied to the surface of the electrophotographic light-receiving member to measure the probability of cracks occurring in the light-receiving layer. It was found that the electrophotographic light-receiving member had a probability of occurrence of 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 comprehensively 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, changing the way the AlCl, /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> CH4 gas was not used in the upper layer of Example 1, and the fourth
A light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in the table, and the same evaluation was performed. As in Example 1, it was found to be good in terms of spots, roughness, and layer peeling. The effect was obtained.

<Example 4> In Example 1, the PH, /H, and gas cylinders were replaced with He gas (
Change the N2 gas cylinder to a No gas (purity 99.9%) cylinder, change the H gas in the upper layer to He gas, and use No gas. 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 to have good effects in improving spots, roughness, and layer peeling. was gotten.

<Example 5> In Example 1, the PH, /H, and gas cylinders were replaced with Ar gas (
Change the N2 gas cylinder to a NH, gas (purity 99°999%) cylinder,
In the upper layer, H2 gas was changed to Ar gas, CH gas was changed to NH gas, and an electrophotographic light receiving member was manufactured in the same manner as in Example 1 under the manufacturing conditions shown in Table 6, and the same evaluation was performed. As a result, similar to Example 1, good effects were obtained in improving the effects of creases, roughness, and layer peeling.

<Example 6> PH, /H, gas is further used in the upper layer, and the seventh
A light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in the table, and the same evaluation was performed. As in Example 1, it was found to be good in terms of spots, roughness, and layer peeling. The effect was obtained.

<Example 7> In Example 1, the N gas cylinder was changed to a S I F 4 gas (purity 99.999%) cylinder, and B 2 Ha /H2 and S I F 4 gas were further used in the upper layer. An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 8, and the same evaluation was conducted. As in Example 1, it was found to be improved against spots, roughness, and layer peeling. Good effects were obtained.

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

<Example 9> In Example 1, the CH gas cylinder was replaced with Cz H2 gas (
(purity 99.9999%) cylinder, change the N gas cylinder to an NO gas cylinder, and change the CH gas in the upper layer to C=H! An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 10, using NO gas instead of gas, and the same evaluation was performed.
Similar to Example 1, poor effects were obtained in that spots, roughness, and layer peeling were improved.

<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, N gas cylinder was replaced with NH gas (purity 9
9.999%) CH 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 NH 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> In Example 6, the N gas cylinder was replaced with a SiF4 gas cylinder, SiFa gas was further used in the upper layer, and the production conditions shown in Table 13 were used for electrophotography in the same manner as in Example 6. A light-receiving member was prepared and evaluated in the same manner as in Example 6, and as in Example 6, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 13> In the upper layer, B, H, /H, gas, 5t=H6 gas (
A light-receiving member for electrophotography was prepared in the same manner as in Example 9 using 99.99% purity) under the preparation conditions shown in Table 14, and the same evaluation was performed. Good effects were obtained to improve the appearance of spots, roughness, and layer peeling.

<Example 14> PH, /H, gas is further used in the upper layer, and 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 N gas cylinder was replaced with G e Ha gas (
A light-receiving member for electrophotography was produced in the same manner as in Example 1, using G e Ha gas in the upper layer instead of the (purity 99.999%) cylinder, and according to the production conditions shown in Table 16. As a result of the evaluation, as in Example 1, good effects were obtained in improving the effects of creases, roughness, and layer peeling.

<Example 16> In Example 1, the outer diameter of the cylindrical aluminum support was 8.0 mm, 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. Similar to the example work, 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, there were improvements in marks, roughness, and layer peeling. Good effects were obtained.

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

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

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

<Example 21> In Example 16, the mirror-finished cylindrical aluminum support was subsequently exposed to a number of drops in the bearing application, resulting in countless dents on the surface of the cylindrical aluminum support. A so-called surface dimple treatment is applied to create a surface with a cross-sectional shape as shown in Figure 39, C = 50 μm, d.
An electrophotographic light-receiving member was prepared under the same conditions as in Example 16 using a cylindrical aluminum-based support having a diameter of 1 μm, and was evaluated in the same manner as in Example 16. 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 po 1y-3i (H,X) according to the preparation conditions shown in Table 21. A receiving member was prepared in the same manner as in Example 9 and evaluated in the same manner as in Example 9. As in Example 9, good effects were obtained in improving spots, roughness, and layer peeling.

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

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

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

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

Thereafter, in the same manner as in Example 1, each gas was introduced into mass flow controllers 1021 to 1027. However, 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 SiH4 gas, H, gas, AlCl, /
Ha 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 5IH4 gas flow rate was 150SCCM.

The mass flow controllers 1021, 1022 and 1027 were adjusted so that the H2 gas flow rate was 20 SCCM and the A I C1,/He gas flow rate was 4008 CCM. The opening of a main valve (not shown) was adjusted so that the pressure inside the deposition chamber 1101 was 0.6 mTorr while checking a vacuum gauge (not shown). After that, the power of a μW power supply (not shown) is set to 0.5 W/cm', and μW is applied into the plasma generation region 1109 through the waveguide 1103 and the dielectric window 1102.
Electric power was introduced to generate a μW glow discharge, and the formation of the lower layer on the cylindrical aluminum-based support 1107 was started. During the formation of the bottom layer, the SiH4 gas flow rate was 1503CCM
The H gas flow rate is 20SCCM so that the flow rate is constant.
A to increase at a constant rate from 500SCCM to 500SCCM.
IC'1. The mass flow controller 1021.1022.1027 controls the /He gas flow rate so that it decreases at a constant rate from 400SCCM to 80SCCM at 0.01 μm on the support side, and from 80 SCCM to 50 SCCM at 0.01 μm on the upper layer side. When the lower layer with a layer thickness of 0.02 μm was formed, the μW glow discharge was stopped, and the outflow valves 1041 and 1042 were adjusted.
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, 1045 and the auxiliary valve 10
Gradually open 18 and add SiH4 gas, H, gas, B, H,
/H gas was flowed into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, SiH4 gas flow rate is 11005CC,H, gas flow rate is 500SCCMSB = Hs /H = gas flow rate is S
Each mass flow controller 1021.1022.102 so that the iH4 gas flow rate is 200 ppm.
Adjusted with 5. The pressure inside the deposition chamber 1101 is 0.5 mT.
It was adjusted so that it was orr.

After that, the power of a μW power supply (not shown) is set to 0.5 W/cm1, and μ
A W glow discharge was generated to start forming the first layer region of the upper layer on the lower layer, and the first layer region of the upper layer with a layer thickness of 3 μm was formed.

Next, to form the second layer region of the upper layer, the outflow valves 1041, 1042, 1046 and the auxiliary valve 10
Gradually open 18 and add SiH4 gas, H, gas, SiF.
The four gases were flowed into the plasma generation space 11 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, 5
iHa gas flow rate is 7008 CCM, H, gas flow rate is 50
Each mass flow controller 1021.1022 so that the SiF4 gas flow rate is 0SCCM and 30SCCM.
．． Adjusted with 1026. The pressure inside the deposition chamber 1101 is 0.
．． It was adjusted to 5 mTorr. Thereafter, the power of a μW power supply (not shown) is set to 0.5 W/cm'', and a μW glow discharge is generated in the plasma generation chamber 1109 in the same manner as in the lower layer, and the lower layer is exposed to the second layer region of the upper layer. The formation of the second layer region of the upper layer with a layer thickness of 20 μm was started.

Next, to form the third layer region of the upper layer, gradually open the outflow valves 1041, 1043 and the auxiliary valve 1018 to add 5iHa gas, CH.

Gas was caused to flow into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time S
i Ha gas flow rate is 150SCCM.

Each mass flow controller 1021 and 1023 was adjusted so that the CHa gas flow rate was 5008 CCM. The pressure inside the deposition chamber 1101 was 0.3 mTorr. After that, the power of the μW power supply (not shown) was increased to 0.5W/cm"
A μW glow discharge was generated in the plasma generation region 1109, and a third layer region of the upper layer having a layer thickness of 1 μm was formed on the second layer region of the upper layer.

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

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

<Example 24> An electrophotographic light-receiving member was produced in the same manner as in Example 9 under the production conditions shown in Table 23, and the same evaluation was performed. A good effect was obtained that improved the results.

<Example 25> This electrophotographic light-receiving member was produced in the same manner as in Example 10 under the production conditions shown in Table 24 and evaluated in the same manner as in Example 10. A good effect was obtained that improved the results.

<Example 26> An electrophotographic light-receiving member was produced in the same manner as in Example 11 under the production conditions shown in Table 25 and evaluated in the same manner as in Example 11.

゛A good effect was obtained in improving roughness and tank peeling.

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

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

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

<Example 30> An electrophotographic light-receiving member was produced in the same manner as in Example 4 under the production conditions shown in Table 29 and evaluated in the same manner as in Example 4.

A good effect of improving roughness and layer peeling was obtained.

<Example 31> An electrophotographic light-receiving member was produced in the same manner as in Example 6 under the production conditions shown in Table 30 and evaluated in the same manner as in Example 6.

A good effect of improving roughness and layer peeling was obtained.

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

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

Table 1 Table 2 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8 Table 9 Table 10 Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 17 Table 18 Table 19 Table 20 Table 21 Table 22 Table 23 Table 24 Table 25 Table 26 Table 27 Table 28 Table 29 Table 30 Table 31 Table 32 [Effects of the invention] By making the electrophotographic light-receiving member of the present invention have the specific layer structure as described above, all the problems in the conventional electrophotographic light-receiving member composed of A-3i can be solved, and in particular, Extremely excellent electrical and optical properties,
Indicates photoconductive properties, image properties, durability and use environment properties.

In particular, in the present invention, 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.

Furthermore, image defects and non-contamination may occur due to relatively short-term impact mechanical pressure applied to electrophotographic light-receiving members.
3i CH,
It can alleviate stress caused by differences in thermal expansion coefficients of i(H,X) films, prevent cracks and peeling of Non-5i(H,X) films, and improve productivity. .

In particular, by containing atoms (CM) that control conductivity in the layer region in contact with the lower layer in the upper layer, charge injection properties or charge injection blocking properties between the upper layer and the lower layer can be selectively controlled. It is possible to improve the image characteristics such as roughness and spots, and it is possible to stably and repeatedly obtain high-quality images with clear halftones and high resolution. Durability is also improved.

[Brief explanation of the drawing]

FIG. 1 is a schematic block diagram for explaining the layer structure of a light-receiving member for electrophotography according to the present invention. FIG. 2 is a schematic block diagram for explaining the layer structure of a conventional light-receiving member for electrophotography. , FIGS. 3 to 8 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. Regarding FIG. 1, a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method, 100...the electrophotographic light-receiving member 101 of the present invention.
...... Aluminum-based support 102 ...
...... Photoreceptive layer 103 ......
...Lower layer 104...
... Upper layer 105 ...... Regarding the free surface in Fig. 2, 200 ... Conventional electrophotographic light receiving member 201 ...
・Dispute... Aluminum support 202...
...Photosensitive layer 203 made of A-3i...
...Free surface in Fig. 37, 1000... Deposition device 1001 using RF glow discharge decomposition method... Deposition chamber 1005
... Cylindrical aluminum support 1008 ...
......Gas introduction pipe 1009...
......Gas release hole 1012...High frequency matching box 1014...Heating heater 1015...Leak valve 101
6・・・・・・・・・・ Main valve 1017...
Fight...fist...vacuum gauge 1018...
..... Auxiliary valve 1020 ..... Raw material gas supply device 1021 to 1027 ... - Mass flow controller 1031 to 1037 ..... Gas inflow valve 1041
~1047...Gas outflow valve 1051~105
7... Valve 1061 to 1067 of raw material gas cylinder... Pressure regulator 1071
~1077... Raw material gas cylinder 1078...
. . . Sealed container for raw materials In FIGS. Room 1102
・・・・・・Contest・・・Dielectric window 1103...
...... Waveguide section 1107 ... Cylindrical aluminum support 1109 ... Plasma generation region 1010 ......・Gas introduction pipe man 5th 1st 40th 6th old. □cuCΔ3 C62c C6/ Figure 11 Figure 13 Old 120 14th Old - 27th '? Figure 2q No. 2S exit No. 30.

Claims (4)

[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 made 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; and a non-single-crystalline material containing at least one of halogen atoms, and an upper layer containing atoms for controlling conductivity in a layer region in contact with the lower layer. Receptive member. (2) The light-receiving member according to claim 1, wherein the atom that controls conductivity is an atom belonging to Group III of the periodic table. (3) The light-receiving member according to claim 1, wherein the atom that controls conductivity is an atom belonging to Group V of the periodic table, excluding nitrogen atoms. (4) The light-receiving member according to claim 1, wherein the atom that controls conductivity is an atom belonging to Group VI of the periodic table, excluding oxygen atoms.