JPS63266459A - Photoreceptive member - Google Patents

Abstract

PURPOSE:To improve the adhesion between upper and lower layers constituting a photoreceptive layer by incorporating at least one of Ge and Sn into a layered region of the upper layer kept in contact with the lower layer. CONSTITUTION:A photoreceptive member 100 is obtd. by forming a photoreceptive layer 102 consisting of a lower layer 103 and an upper layer 104 on an Al-based support 101. The layer 103 is made of an inorg. material contg. at least Al, Si and H and has a part contg. the atoms distributed ununiformly in the thickness direction. The layer 104 is made of an Si-based non-single crystalline material contg. H and/or halogen and contains at least one of Ge and Sn in a layered region kept in contact with the layer 103. The adhesion between the layers 103, 104 is improved, the occurrence of image defects and the peeling of the layer 104 are prevented and the durability of the member 100 is improved.

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 S/N ratio [photocurrent (Ip)/dark current (Id)], and are highly sensitive 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-Si) 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-Si. Such a light-receiving member for electrophotography is generally produced by heating an aluminum support 201 to 50°C to 350°C, and then forming a film on the support by a film forming method such as vapor deposition, thermal CVD, plasma CVD, or sputtering. A photosensitive layer 202 made of A-Si is created.

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

[Problem that the invention seeks to solve]

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

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

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

Furthermore, when the electrophotographic light receiving member comes into contact with foreign matter that has entered the electrophotographic device, or when the electrophotographic light receiving member comes into contact with the electrophotographic device itself or maintenance tools during maintenance of the electrophotographic device, There have been problems in that the durability of the electrophotographic light-receiving member is impaired due to the occurrence of image defects and the occurrence of peeling of the A-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-8i film, resulting in a reduction in productivity and yield.

Therefore, while efforts are being made to improve the properties of the A-8i material itself, when designing an electrophotographic light receiving member, it is important to consider the overall structure of the electrophotographic light receiving member so that all of the above-mentioned problems are solved. It is necessary to make improvements from this perspective.

[Means and effects for solving the problems] The electrophotographic light-receiving member of the present invention has an aluminum support and a multilayer light-receiving layer exhibiting photoconductivity on the support. In the light-receiving member, the light-receiving layer contains fewer aluminum atoms (both aluminum atoms) than the support side.
A1), is composed of an inorganic material (hereinafter abbreviated as rAlsiHJ) containing silicon atoms (Si), and hydrogen atoms (H), and is composed of the aluminum atoms (A1) and silicon atoms (S
i) and hydrogen atoms (H) in a non-uniform distribution in the layer thickness direction;
) as the base, hydrogen atom (H) and halogen atom (X
) (hereinafter referred to as rNon-3i (H.

(abbreviated as X) J), and germanium atoms (Ge) and tin atoms (
It is characterized by comprising an upper layer containing at least one of Sn).

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

In particular, by containing aluminum atoms (A1), silicon atoms (S), and especially hydrogen atoms (H) in a non-uniform distribution state in the layer thickness direction in the lower layer, the relationship between the aluminum support and the upper layer is improved. This improves the injection properties of charge (photocarriers) between the aluminum support and the upper layer, and improves the structural continuity of the constituent elements between the aluminum support and the upper layer, which reduces image characteristics such as roughness and spots. It is possible to stably and repeatedly obtain high-quality images with clear halftones and high resolution.

Furthermore, image defects may occur due to a relatively short impact mechanical pressure applied to a light receiving member for electrophotography.
-5i (H,
It can alleviate the stress caused by the difference in thermal expansion coefficient of the i(H,X) film, prevent cracks and peeling of the Non-8i(H,X) film, and improve productivity. .

In particular, by containing at least one of germanium atoms (Ge) and tin atoms (Sn) in the layer region in contact with the lower layer in the upper layer, the adhesion between the upper layer and the lower layer can be further improved. , occurrence of image defects and N
This prevents the on-5i (H,X) film from peeling off and improves its durability. Furthermore, even if long-wavelength light such as a semiconductor laser is used as a light source for image exposure in an electrophotographic device, the long-wavelength light that cannot be absorbed between the surface side of the upper layer and the lower layer side is highly efficient. Since the light is absorbed, interference phenomena due to reflection of long wavelength light at the interface between the upper layer and the lower layer and/or the surface of the support can be significantly prevented, and image quality can be dramatically 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]

Hereinafter, the electrophotographic light receiving member of the present invention will be described in detail 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 use as an electrophotographic light receiving member, and has the aluminum atoms (A1) and silicon atoms (S i ). and a lower layer 103 having a portion containing hydrogen atoms (H) in a non-uniform distribution state in the layer thickness direction, and non-3i (H, atom(
and an upper layer 104 containing at least one of Sn atoms (Ge) and tin atoms (S.sub.n). 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, A1-Cu, etc., which are standardized or registered as wrought materials, castings, die castings, etc.
Al-Mn series, Al-5i series, Al-Mg series, Al-M
Alloys with compositions such as g-8i series, Al-Zn-Mg series, etc.
l-Cu-Mg type (duralumin, similar duralumin, etc.)
, Al-Cu-5i system (Rautal etc.), Al-Cu-
Contains Ni-Mg type (Y alloy, RR gold alloy), aluminum powder sintered body (SAP), etc.

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

Examples of pure aluminum include JISL100,
Si and Fe 1.0 weight 1% or less, Cu O, 05-0
．． 20% by weight, Mn O, 05% by weight or less, Zn
Al may be 0.10% by weight or less, and Al may be 99.00% by weight or more.

As the Al-Cu-Mg system, for example, JIS 2017, SiO, 05 to 0.20% by weight, Fe 0.7% by weight or less, Cu 3.5 to 4.5% by weight, Mn, 0.40 to
1.0% by weight, Mg 0.40-0.8% by weight, Zn
Examples include O, 25% by weight or less, Cr O, 10% by weight or less, and the balance A1.

As the Al-Mn system, for example, JIS3003, Si
0.6% by weight or less, Fe0.7% by weight or less, CuO
, 05-0.20% by weight, Mn 1.0-1.5% by weight
, Zn 0.10% by weight or less, and A1 balance.

As the Al-5i system, for example, JIS4032 Si
11.0 to 13.5% by weight, Fe 1.0% by weight or less, C
uO, 50-1.3% by weight, MgO, 8-1.3% by weight, ZnO, 25% by weight or less, CrO, 10
% by weight or less, NiO, 5 to 1.3% by weight, balance A1.

As the Al-Mg system, for example, JIS5086, 5
iO 140% by weight or less, Fe O, 50% by weight or less,
CuO, 10% by weight or less, Mn 0.20-0.
7% by weight, Mg3.5-4.5% by weight, ZnO,2
5% by weight or less, CrO, 05-0.25% by weight, Ti
0.15% by weight or less, the remainder being AI.

Furthermore, Si 0.50% by weight or less, FeO,
25% by weight or less, CuO, 04-0.20% by weight,
Mn 0.01-1.0% by weight, MgO, 5-10
Weight%, ZnO, 03 to 0.25% by weight or less, Cr
0.05-0.50% by weight, Ti or TrO,
05 to 0.20% by weight, 1.0 cc or less per 100 grams of H, At, and the balance of A1.

Furthermore, Si 0.12% by weight or less, Fe0.1
5% by weight or less, Mn 0.30% by weight or less, MgO
, 5-5.5% by weight, ZnO, 01-1.0% by weight
Below, Cr0.20% by weight or less, ZrO, O1~0
．． 25% by weight or less, the remainder being A1.

As the Al-Mg-8i system, for example, JIS6063, Si 0.20 to 0.6% by weight, FeQ, 35% by weight or less, Cu 0.10% by weight or less, Mn 0.10
Weight% or less, MgO, 45-0.9% by weight, ZnO
, 10% by weight or less, Cr 0.10% by weight or less, Ti
Examples include O, 10% by weight or less, and the remainder A1.

As the Al-Zn-Mg system, for example, JIS7NO1, Si0.30% by weight or less, FeO, 35% by weight or less, CuO, 20% by weight or less, MnO, 20~
0.7% by weight, Mg 1.0-2.0% by weight, Zn 4.
0 to 5.0% by weight, CrO, 30% by weight or less, Ti
Examples include: 0.20% by weight or less, ZrO, 25% by weight or less, Vo, 10% by weight or less, and the remainder 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 cutting, etc., the free machinability of the aluminum alloy is improved by coexisting magnesium and/or copper in the aluminum alloy.

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

When 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. The lower layer in the present invention is composed of an inorganic material containing a small amount of aluminum atoms (AI), silicon atoms (Si), and hydrogen atoms (H) as constituent elements.

Aluminum atoms (A1), silicon atoms (Si), and hydrogen atoms (H) contained in the lower layer are uniform throughout the entire layer area of the lower layer (although they are contained, their concentration is small in the layer thickness direction). There are parts where the distribution concentration is non-uniform.However, in the in-plane direction parallel to the surface of the support, it is evenly distributed and evenly contained, which makes the properties uniform in the in-plane direction. It is also necessary from

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

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

3 to 8 show aluminum atoms (Al
) 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, tll indicates the position of the end surface of the lower layer on the support side, and 1T indicates the position of the end surface of the lower layer on the support side. The position of the end face of the lower layer is shown. That is, the lower layer containing atoms (A1) is formed from the t, side toward the t layer side.

FIG. 3 shows a first typical example of the distribution state of atoms (A1) contained in the lower layer in the layer thickness direction.

In the example shown in FIG. 3, the distribution concentration C of the contained atoms (A1) is from position t to position ts+, which is the concentration CS+
A distribution state is formed in which the concentration Cs decreases in a -order function from the position tel to the position t7, and reaches the concentration Cs2 at the position t7.

In the example shown in FIG. 4, the distribution concentration C of the contained atoms (Al) is the concentration C4 from position t6 to position t7.
The concentration C decreases linearly from 1 at position ta.
42 is formed.

In the example shown in FIG. 5, the distribution concentration C of the contained atoms (A1) is at position 1. The concentration CI reaches position t7.
A distribution state is formed in which the concentration gradually and continuously decreases from l+ to reach the concentration C112 at position t7.

In the example shown in FIG. 6, the distribution concentration C of the contained atoms (A1) is from position t to position tel, which is the concentration Cat.
A distribution state is formed in which the concentration decreases in a negative order function from the concentration C6 from the position ts+ to the position ta, and reaches the concentration C6m at the position t7.

In the example shown in FIG. 7, the distribution concentration C of the contained atoms (A1) takes a constant value of concentration C71 from position t to position tel, and gradually increases from concentration C72 from position tel to position t7. The distribution state is such that the concentration decreases continuously to reach the concentration Cys at position 11.

In the example shown in FIG. 8, the distribution concentration C of the contained atoms (A1) is from the position t to the concentration C11 up to the position t7.
The concentration C gradually decreases continuously from
A distribution state such as sx is formed.

As described above with reference to FIGS. 3 to 8, some typical examples of the distribution state of atoms (A1) contained in the lower layer in the layer thickness direction, in the present invention, on the support side,
It is preferable if it contains silicon atoms and hydrogen atoms and has a portion where the distribution concentration C of atoms (A1) is high, and has a portion where the distribution concentration C is considerably lower than that on the support side at the interface t7. examples are formed. In this case, the maximum value Cmax of the distribution concentration of atoms (A1) is preferably 1
It is desirable that the layer be formed in such a manner that the distribution state can be such that the content is at least .degree. atomic %, 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 axis represents silicon atoms (S
i), hydrogen atom (H) (hereinafter these will be collectively referred to as "atom (
SH) Abbreviated as J. However, the distribution state of silicon atoms (Si) and hydrogen atoms (H) in the layer thickness direction may be the same or different), the vertical axis indicates the layer thickness of the lower layer, and tll is the position of the end surface of the lower layer on the support side,
I7 indicates the position of the end face of the lower layer on the upper layer side. That is, the lower layer containing atoms (SH) is formed from the I8 side toward the I7 side.

FIG. 9 shows a first typical example of the distribution state of atoms (SH) contained in the lower layer in the layer thickness direction.

In the example shown in FIG. 9, the distribution concentration C of the contained atoms (SH) is from the position t to the position te+.
Increased numerically by one hour from I+, position t from position ts+
Up to A, a distribution state is formed in which the concentration takes a constant value of 0.2.

In the example shown in FIG. 10, the distribution concentration C of the contained atoms (SH) is the concentration CIo from the position ts to the position t7.
Increasing linearly from l to position t. At the concentration C
A distribution state of 3°2 is formed.

In the example shown in FIG. 11, the distribution concentration C of the contained atoms (SH) gradually and continuously increases from the concentration CIll from the position tll to the position t7, and becomes the concentration C1□ at the position tT. It forms a similar distribution state.

In the example shown in FIG. 12, the distributed concentration C of the contained atoms (SH) increases numerically from the concentration C121 for one hour from the position tIl to the position t1,1, and at the position t121 the concentration C3!2 Then, from position t2゜1, position 1T
Until then, a distribution state is formed that takes a constant value of concentration CI21.

In the example shown in FIG. 13, the distribution concentration C of the contained atoms (SH) gradually and continuously increases from the concentration C111 until reaching the position t, then the position t+a, and then increases from the concentration C111 to the position t88. The concentration becomes CI82 at the position tISl and the position tT
Until then, a distribution state is formed that takes a constant value of concentration CIss.

In the example shown in FIG. 14, the distribution concentration C of the contained atoms (SH) is the concentration C from position tn to position t7.
A distribution state is formed in which the concentration increases gradually and continuously from 141 to reach a concentration CI42 at position t7.

In the example shown in FIG. 15, the distribution concentration C of the contained atoms (SH) is substantially zero from position t8 to position t, 6° (here, substantially zero means an amount below the detection limit). (the meaning of "substantially zero" hereinafter is also the same), the concentration gradually increases to C+8+ at position t1,1, and the concentration C1 increases from position t ISl to position 11.
A distribution state is formed that takes a constant value of 52.

In the example shown in FIG. 16, the distribution concentration C of the contained atoms (SH) gradually increases from substantially zero from position t8 to position t, and at position tT the concentration CI61
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, on the support side, aluminum Contains an atom (A1), and an atom (SH)
has a low distribution concentration C, and at the interface tT,
A preferable example is formed when the lower layer is provided with a distribution state of atoms (SH) having a portion where the distribution concentration C is considerably higher than that on the support side. In this case, the distribution state can be such that the maximum value Cmax of the distribution concentration of the sum of atoms (SH) is preferably 10 atomic % or more, more preferably 30 atomic % or more, and optimally 50 atomic % or more. It is desirable that the layers be formed like this.

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

In the present invention, hydrogen atoms (H) contained in the lower layer
The content 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 A I S i H is formed by, for example, using the same vacuum deposition film forming method as the upper layer described later, and the numerical conditions of the film forming parameters are appropriately set so as to obtain the desired characteristics. and created. Specifically, for example, glow discharge method (low frequency CVD, high frequency CVD)
It can be formed by various thin film deposition methods such as AC discharge CVD such as D or microwave CVD, or DC discharge CVD, etc.), ECR-CVD, sputtering, vacuum evaporation, ion blating, and photo-CVD. Can be done. 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 producing electrophotographic light-receiving members with specific characteristics, and it is easy to introduce hydrogen atoms together with aluminum atoms and silicon atoms. method, sputtering method, and ion blating method are suitable. These methods may be used in combination within the same device system. For example, by the glow discharge method,
In order to form the lower layer composed of Al5iH, basically a raw material gas for supplying A1 that can supply aluminum atoms (A1) and a Si gas that can supply silicon atoms (Si) are used.
A supply gas and an H supply gas capable of supplying hydrogen atoms (H) are introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated within the deposition chamber to generate a predetermined amount of hydrogen. A layer made of Al5iH may be formed on the surface of a predetermined support.

When forming by sputtering method, for example, Ar5
A target made of A1, S in an atmosphere of an inert gas such as He or a mixed gas based on these gases.
using a target composed of i or A1 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 A1 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, aluminum atoms (A1) and silicon atoms (Si) (
From now on, these will be collectively referred to as "atomic (ASH) J".
In order to form a layer having a desired distribution state (depth profile) in the layer thickness direction by changing the distribution concentration C of ) The raw material gas for supply is introduced into the deposition chamber while the gas flow rate is appropriately changed according to a desired rate of change curve.

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

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

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

Examples of substances that can be used as the raw material gas for supplying A1 used in the present invention include AlCl5. AlBr3゜AIi,A
I (CH,), CI, AI (CHI),.

AI (OCHs)s, AI (C2Hs)3. AI
(OCz Hs) s + AI (i C4H9
)3 + AI(i-CiHt)s, AI(C3H
7)3. AI(QC4H,'), etc. can be cited as one that can be effectively used. Further, these raw material gases for supplying AI may be diluted with gases such as H2, He, Ar, Ne, etc. as necessary.

Substances that can be used as the raw material gas for supplying Si used in the present invention include S i H4 and S i 2 Ha.

Si, sHa, 5i4H+. Silicon hydrides (silanes) in a gaseous state or that can be gasified are mentioned as those that can be effectively used, and furthermore, they are easy to handle during layer creation work,
S I Ha, 312 in terms of St supply efficiency, etc.
Ha is preferred. In addition, these raw material gases for Si supply may be adjusted to Hz, He,
It may be used after being diluted with a gas such as Ar or Ne.

Substances that can be used as the raw material gas for hydrogen supply used in the present invention include H2 or SiH4+ 5i
zHs, 5isHs, 5i4H+. Silicon hydrides (silanes) such as the following are mentioned as those that can be effectively used.

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

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

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

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

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

In the present invention, when the lower layer made of Al5iH is created by the glow discharge method, the optimal range of discharge power supplied into the deposition chamber is selected as appropriate according to the layer design, but usually it is 5X10"-'~10W/ crr?,
Preferably 5 X 10-' to 5 W/c rr? .

Optimally I x 10-” to 2 x 10-’W/
It is preferable to set the value to "cm".

In the present invention, the above-mentioned desirable numerical ranges for the gas pressure in the deposition chamber, the support temperature, and the discharge power supplied to the deposition chamber for creating the lower layer include the above-mentioned ranges, but these layer creation factors are usually It is preferable to determine the optimal value of the underlayer formation factor based on mutual and organic relationships, rather than being determined independently and separately, and to form the underlayer having desired properties.

- clothes 1 The lower layer in the present invention is Non-3i (H.

X) and has desired photoconductive properties.

In the present invention, at least the layer region of the upper layer in contact with the lower layer contains germanium atoms and/or tin atoms, and if necessary, atoms (M) and/or carbon atoms (C) and /or nitrogen atom (N
) and/or an oxygen atom (0). In addition, other layer regions of the upper layer include atoms that control conductivity (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge), and tin atoms ( Sn
) of carbon atoms (C
), nitrogen atoms (N), and oxygen atoms (0).

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

Atoms (M), carbon atoms (C), nitrogen atoms (N), oxygen atoms (0), germanium atoms (Ge
), when at least one type of tin atom (S n) is contained in the center, the conductivity controlling atom (M), carbon atom (C), nitrogen atom (N), oxygen atom (O), germanium Atoms (Ge) and tin atoms (Sn) may be uniformly distributed in the layer region, or they may be uniformly contained in the layer region, but may be distributed uniformly in the layer region, but may There may be a portion containing it in a non-uniformly distributed state.

However, in any case, in the in-plane direction parallel to the surface of the support, it is uniformly distributed and evenly distributed (this is necessary from the point of view of making the properties uniform in the in-plane direction). be.

In addition, atoms (M) that control conductivity (hereinafter referred to as "atoms (M)"
(abbreviated as “layer region (M)”) (hereinafter referred to as “layer region (M)
) and a layer region containing carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0) (hereinafter abbreviated as [atoms (CNO) J) (abbreviated as (CNO)J), germanium atom (abbreviated as
Ge) and/or tin atom (Sn) (hereinafter referred to as “atom (
The layer region (hereinafter abbreviated as "layer region (GS,')J") that is in contact with at least the lower layer of the layer region containing the layer region (abbreviated as "GS, ') J" may be substantially the same layer region. ,
At least a part of the surface side of the layer region (GS) may be shared.

In addition, a layer region containing atoms (GS) other than the layer region (GS, ) (hereinafter abbreviated as "layer region (GS7)J", and layer region (GS, ) and layer region (GST) collectively referred to as " Layer area (
GS) J), layer region (M), and layer region (C
(NO) may be substantially the same layer area, or may share a small (part of each layer area),
It is not necessary that the respective layer regions are substantially shared.

17 to 36 show typical examples of the distribution state of atoms (M) contained in the layer region (M) in the layer thickness direction in the upper layer of the electrophotographic light-receiving member of the present invention. Typical example of the distribution state of atoms (CNO) contained in the layer region (CNO) in the layer thickness direction, Typical example of the distribution state of atoms and children (GS) contained in the layer region (GS) in the layer thickness direction This is what is shown. (Hereinafter, layer region (M), layer region (CNO), and layer region (GS) will be referred to as "layer region (Y)," and atom (M), atom (CNO), and atom (GS) will be represented as "layer region (Y)."do"
Atom (Y)". Therefore, FIGS. 17 to 36 show typical examples of the distribution state of atoms (Y) contained in the layer region (Y) in the layer thickness direction. (M), layer region (CNO), layer region (GS)
If they are substantially the same layer area, a single layer area (Y) is included in the upper layer, and if they are not substantially the same layer area, multiple layer areas (Y) are included in the upper layer. Teeth are broken).

17 to 36, the horizontal axis shows the distribution concentration C of atoms (Y), the vertical axis shows the layer thickness of the layer region (Y), and t is the end face of the layer region (Y) on the lower layer side. The position of , and 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 t7 side.

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

In the example shown in FIG. 17, the distribution concentration C of the contained atoms (Y) is the concentration C from position tll to position t7.
17, a distribution state is formed in which the concentration increases gradually and continuously to reach a concentration C112 at position 11.

In the example shown in FIG. 18, the distribution concentration C of the contained atoms (Y) increases numerically from the concentration CIII for one hour from the position t8 to the position tIII, and reaches the concentration C182 at the position t, 81. , from position t181 to position t7, a distribution state is formed that takes a constant value of concentration C18.

In the example shown in FIG. 19, the distribution concentration C of the contained atoms (Y) is a constant value of concentration CIII from position tIl to position t191, and from position t1,1 to position t1.2. A distribution state is formed in which the concentration gradually and continuously increases from C18 until the concentration reaches CIO2 at positions t1 and 2, and takes a constant value of concentration C1 from position t1° to position 11.

In the example shown in FIG. 20, the distribution concentration C of the contained atoms (Y) is from position tll to position t. The concentration becomes a constant value of C2゜1 until reaching 1, and the concentration becomes a constant value of C202 from position t2゜1 to position t2゜2,
From position t2°2 to position tr, a distribution state is formed in which the concentration takes a constant value of C8°.

In the example shown in FIG. 21, the distribution concentration C of the contained atoms (Y) is at position 1. From this point up to position 11, the concentration is C2,1.
A distribution state is formed such that the value is a constant value.

In the example shown in FIG. 22, the distribution concentration C of the contained atoms (Y) is at position 1. From position t2□.

Until then, a constant value of density C2!1 is taken as position ff1jz2
A distribution state is formed in which the concentration gradually and continuously decreases from C222 from + to position 11, and reaches a concentration C2° at position 1T.

In the example shown in FIG. 23, the distribution concentration C of the contained atoms (Y) is as follows from position tB to position 1T.
, , gradually and continuously decreases, forming a distribution state in which the concentration becomes C18 at position 11.

In the example shown in FIG. 24, the distribution concentration C of the contained atoms (Y) is C3 from the position tIl to the position t241.
The distribution density C gradually and continuously decreases from 242 to position t and 41 to Ht t, and the distribution density C becomes substantially zero at position ta (here, it becomes substantially zero). is a case where the amount is less than the detection limit, and the meaning of "substantially zero" hereinafter is also the same).

In the example shown in FIG. 25, the distribution concentration C of the contained atoms (Y) is from the position t to the concentration C2 up to the position ta.
A distribution state is formed in which the distribution concentration C gradually and continuously decreases from B'l and becomes substantially zero at position ta.

In the example shown in FIG. 26, the distribution concentration C of the contained atoms (Y) is from position t8 to position t, and from position t8 to position 61 is the concentration C2.
It takes a constant value of 61 at position t, and decreases linearly from the concentration C281 from 6° to position t7, and then reaches position t.
A distribution state is formed such that the concentration is C36 in A.

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

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

A distribution state is formed in which the concentration takes a constant value C28 up to the point t281 and decreases linearly from the concentration C2,1 from position t281 until the concentration C282 at the position t7.

In the example shown in FIG. 29, the distribution concentration C of the contained atoms (Y) is the concentration C3 from position t8 to position tT.
A distribution state is formed in which the concentration gradually and continuously decreases from 1° to a concentration of C2° at position ta.

In the example shown in FIG. 30, the distribution concentration C of the contained atoms (Y) takes a constant value of concentration C1° from position tll to position tA01, and from position t301 to position tA01.
Up to 7, the concentration decreases from C1° in a -order function, forming a distribution state in which the concentration reaches C1°3 at position 11.

In the example shown in FIG. 31, the distribution concentration C of the contained atoms (Y) increases gradually and continuously from the concentration Cil+ from the position t to the position t8,1 until the concentration C112 at the position tA11. Then, from position t,,1, position t7
Up to this point, a distribution state is formed in which the concentration takes a constant value of C318.

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

In the example shown in FIG. 33, the distribution concentration C of the contained atoms (Y) is substantially zero from position tll to position t8$1 (here, substantially zero means less than the detection limit amount). (The meaning of "substantially zero" hereinafter is also the same)
The concentration C3 gradually increases from 331 to 331.
1, and a distribution state is formed in which the concentration takes a constant value of C33□ from position tssl to position ta.

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 tT, and reaches a concentration C141 at position 11. 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 csat from position t to position t8,1, and then reaches position t381.
A distribution state is formed in which the concentration takes a constant value of C162 up to position t7.

In the example shown in FIG. 36, the distribution concentration C of the contained atoms (Y) is C86 from the position tl+ to the position ta.
, the concentration C increases at the position t7 in a -order function.
362 is formed.

Examples of the atoms (M) that control the conductivity include so-called impurities in the semiconductor field. (abbreviated as "group atom") or n
Periodic table V excluding the nitrogen atom (N) which gives type conductivity properties
(hereinafter abbreviated as "group ■ atoms") and atoms belonging to group ■ of the periodic table, excluding oxygen atoms (0) (hereinafter abbreviated as "group ■ atoms")
Hereinafter abbreviated as "Group I atoms") will be used. Specifically, the Group Ⅰ atoms include B (boron), A1 (aluminum), Ga (gallium), In (indium), TI (
thallium), among which B, AI, and Ga are particularly preferred. Specifically, the Group V atoms include P (phosphorus), As (
Arsenic), Sb (antimony), Bi (bismuth), etc., with P and As being particularly preferred. As group ■ atoms,
Specifically, there are S (sulfur), Se (selenium), Te- (tellurium), Po (polonium), etc., with S and Se being particularly preferred. In the present invention, the conductivity type and/or conductivity can be mainly controlled by containing a group (I) atom, a group V atom, or a group (IV) atom as an atom (M) that controls conductivity in the layer region (M). Controlling effects and/or
Alternatively, it is possible to obtain the effect of improving the charge injection property between the layer region (M) and the layer region other than the layer region (M) of the upper layer. The content of atoms (M) that control conductivity contained in the layer region (M) is preferably 1×10−3 to 5×
10′ atom 1) More preferably lXl0−”~I
X 10' atoms ppm, optimally lXl0-' ~5
It is desirable that the content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (0), which will be described later, in the layer region (M) is 1Xl0" atoms ppm or less. In this case, the content of atoms (M) that control conductivity contained in the layer region (M) is preferably 1-x 10-'' to 1 x 103 atomic ppm, and carbon atoms (C) and/
Or, if the content of nitrogen atoms (N) and/or oxygen atoms (0) exceeds 1 x 10s atoms ppm, the content of atoms (M) that controls conductivity is preferably lX
It is desirable that the content be 10-' to 5X10' atomic ppm.

In the present invention, carbon atoms (C) are added to the layer region (CNO).
and/or by containing nitrogen atoms (N) and/or oxygen atoms (0), mainly to increase the dark resistance and/or hardness and/or to control the spectral sensitivity and/or to control the layer region (CNO) and the upper part. The layer area of the layer (C
It is possible to obtain the effect of improving the adhesion between layer regions other than NO). The content of carbon atoms (C) and/or nitrogen atoms (N) and/or oxygen atoms (○) contained in the layer region (CNO) is preferably 1 to 9X
10' atom pI) m%, preferably lXl0' to 5X
10' atom pI) m% optimally from 1 x 102 to 3 x 10I
' It is preferable to set it as atomic ppm. Especially when aiming for high dark resistance and/or high hardness, preferably 1xl
It is desirable that the content is 1 x 10 atomic ppm to 9 x 10 5 atomic ppm, and preferably 1 x 10 2 to 5 atomic ppm when controlling the spectral sensitivity.
It is preferable that X10' atoms ppm.

In the present invention, by containing germanium atoms (Ge) and/or tin atoms (Sn) in the layer region (GS), it is possible to mainly control the spectral sensitivity, and in particular, to control the spectral sensitivity, and in particular to use a semiconductor laser or the like as an image exposure source of an electrophotographic device. The effect of improving the long wavelength light sensitivity when using long wavelength light and/or the effect of preventing the appearance of interference phenomena, and/or the effect of improving the adhesion between the layer region (GS, ) and the lower layer and /
Alternatively, it is possible to obtain the effect of improving the adhesion between the layer region (GS) and the layer region other than the layer region (GS) of the upper layer. Germanium atoms (
The content of (Ge) and/or tin atoms (Sn) is preferably 1 to 9.5X105 atomic ppm, more preferably 1X10'' to 8X105 atomic ppm, optimally 5
It is desirable that the content be X10' to 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 1
The content of halogen atoms (X) is preferably 1 to 4 x 1 ppm.
It is desirable that the content be 0' 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.
When X10' atomic ppm or less, the content of hydrogen atoms (H) or the sum of hydrogen atoms (H) and halogen atoms (X) is desirably set to IX10'' to 4X10' atomic ppm.

Furthermore, if the upper layer is composed of polycrystalline material,
The content of hydrogen atoms (H) or the sum of hydrogen atoms (H) and halogen atoms (X) contained in the upper layer is preferably 1X10" to 2X10' atomic ppm, and non-containing When composed of crystalline material, preferably l
It is desirable that Xl0' to 7×10 6 atomic ppm.

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

For example, Non-3i, (H
, X), basically a Si supply gas capable of supplying silicon atoms (Si);
N supply gas that can supply hydrogen atoms (H) and/or X supply gas that can supply halogen atoms (X), and X that can supply atoms (M) that control conductivity as necessary
Supply gas and/or C supply gas capable of supplying carbon atoms (C) and/or N supply gas capable of supplying nitrogen atoms (N) and/or C supply gas capable of supplying oxygen atoms (0) gas and/or germanium atoms (G
A Ge supplying gas capable of supplying e) and/or a Sn supplying gas capable of supplying tin atoms (Sn) are introduced at a desired gas pressure into a deposition chamber whose interior can be reduced in pressure. A glow discharge may be generated to form a layer made of Non-8i (H,

To form the upper layer composed of Non-5i' (H, X supply gas capable of supplying atoms (M) and/or C supply gas capable of supplying carbon atoms (C) and/or N supply gas capable of supplying nitrogen atoms (N) and/or C that can supply oxygen atoms (0)
Supply gas and/or Ge supply gas capable of supplying germanium atoms (Ge) and/or tin atoms (S
Sn supply gas capable of supplying Sn is introduced at a desired gas pressure into an activation space provided at the front stage of a deposition chamber, the interior of which can be reduced in pressure, separately or together as necessary, 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. No. 8 is placed in a predetermined position on the surface of a support on which a predetermined lower layer is formed.
A layer consisting of i (H,X) may be formed.

To form the upper layer composed of Non-3i (H,
N supply gas capable of supplying H), X 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-8i (H,X) may be formed on the surface of the support.

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

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

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

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

Silicon hydride (silanes) in a gaseous state or that can be gasified, such as S is Hs and 5i4H+o, can be cited as being effectively used. SiH4, Sit H
a is preferred. Also, these S
The raw material gas for i supply is H2, He, Ar,
It may be used after being diluted with a gas such as Ne.

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

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

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, CIF, ClF5. BrF5. Br
F5. Examples include interhalogen compounds such as IFF, IF7°ICI, and IBr.

Preferred examples of silicon compounds containing halogen atoms, so-called halogen atom-substituted silane derivatives include silicon halides such as SiF4,5i2Fs, 5iC1a, and SiBr4.

When a silicon compound containing such a halogen atom is used to form the characteristic electrophotographic light-receiving member of the present invention by a glow discharge method or an HRCVD method, silicon hydride gas is used as the Si supply gas. Non-8i (H,X) containing halogen atoms on the desired support
A top layer consisting of:

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

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 in addition, halogenated gases such as HF, HCI, HBr, and HI Hydrogen, S I Hs F', 'S IH2F2,5iHF
s, SiH2I2, 5iHzC1z, 5tHC1i
, 5IH2Br2, 5iHB r a and other halogen-substituted silicon hydrides, and other gaseous or gasifiable substances 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.

This can also be carried out by coexisting silicon hydride such as S 1 a Hs r S I4 Hlo and silicon or a silicon compound for supplying Si in a deposition chamber to generate a discharge.

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

In order to structurally introduce atoms (M) that control conductivity into the upper layer, for example, group II atoms, group V atoms, or group II atoms, group A raw material for introduction, a raw material for introducing group V atoms, or a raw material for introducing group (III) atoms is placed in a gaseous state in a deposition chamber,
It may be introduced together with other raw materials for forming the upper layer. Materials that can be used as a raw material for introducing group (III) atoms, a raw material for introducing group V atoms, or a raw material for introducing group (III) atoms may be gaseous at room temperature and pressure, or at least under layer-forming conditions. It is desirable to use a material that can be easily gasified. Specifically, as a raw material for introducing a group Ⅰ atom, B2H is used for introducing a boron atom.

B,H,,,B,H,,B,H,,,B,Hl,,B.

Boron hydride such as H1□, B6HI4, BF,, BCl,
.

Examples include boron halides such as BB I3. In addition, AlCl3. GaC15, Ga (CHI) $.

I n CI 3 , T I C1s and the like can also be mentioned.

In the present invention, the raw materials for introducing group (IV) atoms that are effectively used for introducing phosphorus atoms are PH,
Hydrogen north neighbor of P2H, etc., PH, I.

PFs, PF5, PCl5, PCl,, PBrs
.

Examples include halogen north neighbors such as PBr+t and Plm. In addition, As)(s), AsF5, ASC13.

AsBr5, AsF5, SbH,,5bFs +S
bF5, 5bCI, 5bCls, Bias.

BiC]s, BiBrx, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

Hydrogen sulfide (I-
(2S), SF4. SF, SO2, SO2F,
.

CO8, C32, CH, SH, C, H, SH.

C, H4S, (CH,), S, (C,H,), S, and the like, which are in a gaseous state or can be gasified. In addition, SeH2,5eFa, (CHs)xSe, (C2H
s)2Se, TeHz, TeFs.

(CHs) 2 T e, (C2Hs) t
Mention may be made of gaseous or gasifiable substances such as Te.

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

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

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

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

Specifically, as a saturated hydrocarbon, methane (CH4)
, ethane (C,H6), propane (C.

Ha), n-butane (n Ca Hto) + pentane (CfiH, , ), and ethylene hydrocarbons include ethylene (C, H4) and propylene (C, H, ).

Butene-1 (C,H,), Butene-2 (C4Ha).

Isobutylene (C4H,), Pentene (CIIH, )
.

Acetylene (C.

H3), methylacetylene (C, H4), butyne (C4
H6) and the like.

As a raw material gas containing Si, C, and H as constituent atoms, S
i (Cf(s') 4 , Si (C2Hs
) 4 and the like can be mentioned.

In addition to this, in addition to introducing carbon atoms (C), halogen atoms (X) can also be introduced, so CF, CC14
, CH, CF, and other halogenated carbon gases.

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

Mention may be made of gaseous or gasifiable nitrogen such as ammonium azide (NH4N, ), nitrogen compounds such as nitrides and azides. In addition to this, in addition to introducing nitrogen atoms (N), halogen atoms (X) can also be introduced, so nitrogen trifluoride (F, N), nitrogen tetrafluoride (F4N
, ), etc. can be mentioned.

Starting materials that can be effectively used as raw material gases for introducing oxygen atoms (0) include, for example, oxygen (02), ozone (0,), and nitrogen oxide (NO).

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

Nitrogen sesquioxide (N, O,), trinitrogen tetraoxide (N204)
, nitrogen sesquioxide (N, O,), nitrogen dioxide (No□),
Silicon atom (S i), oxygen atom (0) and hydrogen atom (
For example, disiloxane (Hs
SiOS I Hs) r) LilleyClxane (
Examples include lower siloxanes such as Hz SiO3iHs O3iHs ).

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

As a material that can be a source gas for supplying Ge, GeH
a, Ge2Hs, GesHs, GczH+o,
Ges H,,,Geo HI41 Get He
Germanium hydride in a gaseous state or that can be gasified, such as arG e s H18 and Ge s H2°, can be effectively used, especially because of its ease of handling during layer creation work, good Ge supply efficiency, etc. In terms of GeH4
, Ge2He, and GeaHa are preferred.

In addition, GeHF, GeH8Br, GeHsF, G
eHCl5, GeHz C12, GeHsCl, Ge
HB I3 , GeHz Brx , GeH8Br,
GeHl, , GeHz I2. Germanium hydrogenated halides such as GeHs I, GeF4゜GeCl4. Ge
Br4. GeI4, GeF2゜GeC12, GeB
r2. Examples include germanium halides such as Ge I2.

Substances that can be used as raw material gas for Sn supply include SnH.
4, Srz Ha, Sns Hs, 5rzHIQ+
S ns N121 S no HI41 S ny
H161S n s H18, S n *Hz. Sn hydride in a gaseous state or that can be gasified can be effectively used, such as Sn Ha.
+Sn4H, and SrzHa are preferred.

In addition, 5nHFs, 5nHz F2.5nHsF,
5nHCj! s, 5nHz C1! z, 5nHsC
L 5nHBrs , 5nH2Brt , 5nHsB
r, 5nHIa, 5nH2I2, 5nHs I
Hydrogenated tin halides such as S n F a , S
nCl a +SnB ra , Sn 14.5nF
z, 5nC1i.

SnBr2. Sn1. Gaseous or gasifiable substances such as tin halides and the like may also be mentioned as useful starting materials for forming the upper layer.

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

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

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

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

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

The upper layer is Non-9i (H,X) and hydrogen atoms (H
) and/or polycrystalline silicon containing halogen atoms (X) (hereinafter abbreviated as rpoly-3i (H,X)J), various methods can be used to form the layer. There are several methods, such as the following.

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

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

In the present invention, when the upper layer made of Non-8i (H, 5X 10-5~10W/
Cm3, preferably 5 x 10-'~5 W/cm
', optimally 1 x 10-3 to 2 x 10 ''W/
It is desirable to set it to cm'.

*Akira[]B+-Matsuiteha-! 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 partially depleting M layers are included, but these layer creation factors are usually independent. are not determined separately, but are based on mutual and organic relationships to form an upper layer with desired properties.
It is desirable to determine the optimal value of the upper layer creation factor.

〔Example〕

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

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

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

1071.1072, 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 airtight container, and 1071 is a SiH4 gas (purity 99.99%) cylinder, and 1072 is a H gas (purity 99.9999%) cylinder. %) cylinder, 1073 is CH, gas (
Purity 99°999%) cylinder, 1074 is G e Ha
Gas (purity 99.999%) cylinder, 1075 is H, B2H diluted with gas (purity 99.999%, hereinafter abbreviated as rB, H, /H2J), 1076 is He gas (purity 99.9 %) cylinder, 1077 is a He gas (purity 99.999%) cylinder, and 1078 is a sealed container filled with AlCl5 (purity 99.99%).

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

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

Next, the reading on the vacuum gauge 1017 is about 1X10-”Torr.
When the auxiliary valve 1018 and outflow valve 104
1-1047 were closed.

After that, SiH4 gas from gas cylinder 1071, H2 gas from gas cylinder 1072, and C from gas cylinder 1073.
H4 gas, GeHa gas from gas cylinder 1074, B from gas cylinder 1075.

Ha / Hz i S, No. from gas cylinder 1076
Gas, He gas from gas cylinder 1077, valve 10
Open and introduce pressure regulators 1061 to 1057.
The pressure of each gas was adjusted to 2Kg/Cm2 using the 1067.

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

The temperature of the cylindrical aluminum-based support 1005 installed in the deposition chamber 1001 was adjusted to 250° C. by the heating heater 1014. A lower layer and an upper layer were formed on the support 1005.

To form the bottom layer, the outflow valves 1041°1042
．． 1047 and auxiliary valve 1018 gradually open.
iH4 gas, H2 gas, AlC1, /He gas is introduced into the deposition chamber 10 through the gas discharge hole 1009 of the gas introduction pipe 1008.
01. At this time, the SiH4 gas flow rate is 5
03CCM, H, gas flow rate is 10S CCMSAIC
Each mass flow controller 1021.1022.1 so that the /He gas flow rate is 1208 CCM.
Adjusted with 027. The pressure inside the deposition chamber 1001 is 0.4
The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the pressure was Torr. After that, R (not shown)
The power of the F power supply was set to 5 mW/cm3, and RF power was introduced into the deposition chamber 1001 through the high frequency matching box 1012 to generate an RF glow discharge and start forming a lower layer on the cylindrical aluminum support. . During the formation of the lower layer, the H2 gas flow rate was changed from 10300M to 200M so that the S i H4 gas flow rate was a constant flow rate of 50SCCM.
AlC1,/ so as to increase at a constant rate in SCCM
The mass flow controller 10 decreases the He gas flow rate from 120SCCM to 40SCCM at a constant rate.
21.1022.1027 adjusted to a layer thickness of 0.05μm
After forming the lower layer, the RF glow discharge was stopped, and the outflow valves 1041, 1042, 1047 and the auxiliary valve 1018 were 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, 1044 and the auxiliary valve 10
Gradually open 18 and add SiHa gas, H, gas, GeH.
A gas was introduced into the deposition chamber 1001 through the gas discharge hole 1009 of the gas introduction pipe 1008. At this time, SiH4
Gas flow rate is 11005CC, H2 gas flow rate is 11005CC
C.C.

Each mass flow controller 1021.1022.102 so that the G e Ha gas flow rate is 50SCCM.
Adjusted with 4. The pressure inside the deposition chamber 1001 is 0.4To
The opening of the main valve 1016 was adjusted while checking the vacuum gauge 1017 so that the temperature was rr. Thereafter, the power of an RF power source (not shown) is set to 10 mW/cm'', and RF power is introduced into the deposition chamber 1001 through the high frequency matching box 1012 to generate an RF glow discharge, and the upper layer is formed on the lower layer. The formation of the first layer region of the upper layer was started. During the formation of the first layer region of the upper layer, the SiH4 gas flow rate was 1100
5CC, H, G e Ha gas flow rate is 0.7 μm on the lower layer side so that the gas flow rate is a constant flow rate of 11005 CC.
In order to obtain a constant flow rate of 508 CCM, the surface side is set to 0.
At 3μm, the mass flow controller 1021.1 is set so that it decreases at a constant rate from 50SCCM to O3CCM.
022° 1024 to form the first layer region of the upper layer with a layer thickness of 1 μm, the RF glow discharge is stopped, and the outflow valves 1041, 1042° 1044 and the auxiliary valve 1018 are closed, and the inside of the deposition chamber 1001 is closed. The gas flow was stopped, and the formation of the first layer region of the upper layer was completed.

Then, to form the second layer region of the upper layer, gradually open the outflow valves 1041, 1042, 1045, 1046 and the auxiliary valve 1018 to release SiH4 gas + H2 gas, B, H, /H, gas.

NO gas was allowed to flow into the deposition chamber 1001 through the gas discharge hole 1009 of the gas introduction pipe 1008 . At this time, S i
Ha gas flow rate is 11005CC,H.

The mass flow controllers 1021, 1022, 1025, and 1026 were adjusted so that the gas flow rate was 110003 CC, B, H, /H, the gas flow rate was 800 ppm for SiH, and the 'No gas flow rate was 10300 M. While checking the vacuum gauge 1017, adjust the pressure inside the deposition chamber 1001 to 0.4 Torr by turning the main valve 101.
Adjusted the aperture of 6. Thereafter, the power of an RF power source (not shown) is set to 10 mW/cm3, and RF power is introduced into the deposition chamber 1001 through the high frequency matching box 1012 to generate an RF glow discharge, and the first layer region of the upper layer is heated. Formation of the second layer area was started on top. During the formation of the second layer region of the upper layer, the SiH4 gas flow rate was 11005C.
C, H, gas flow rate is 100S1005CC,/H, gas flow rate is 800 ppm constant flow rate for SiH4 gas, No gas flow rate is 103 at 2 μm on the lower layer side.
11 μm on the surface side to achieve a constant flow rate of 00M.
Mass flow controller 1021.1022.102 to decrease at a constant rate from 05CC to O8C0M
5.1026 was adjusted, and when the second layer region of the upper layer with a layer thickness of 3 μm was formed, the RF glow discharge was stopped, and
The outflow valves 1041, 1042, 1045, and 1046 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, 1042 and the auxiliary valve 1018 are gradually opened to introduce the S i Ha gas l H2 gas into the gas inlet pipe 1.
008 into the deposition chamber 1001 through the gas discharge hole 1009. At this time, the S i Ha gas flow rate is 300
The mass flow controllers 1021 and 1022 were used to adjust the flow rates of 3CCM, H, and gas to 3003CCM. The pressure inside the deposition chamber 1001 is 0.5 Torr.
Main valve 1 while watching vacuum gauge 1017 so that
Adjusted the aperture of 016. Thereafter, the power of an RF power source (not shown) is set to 15 mW/cm'', and RF power is introduced into the deposition chamber 1001 through the high frequency matching box 1012 to generate an RF glow discharge, and the second layer region of the upper layer is Start forming the third layer region of the upper layer to a layer thickness of 20
Stop the RF glow discharge after forming the third layer region of the upper layer of μm, and also the outflow valve 1041.1042
Then, the auxiliary valve 1018 was 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.

Next, to form the fourth layer region of the upper layer, the outflow valves 1041, 1043 and the auxiliary valve 1018 are gradually opened to supply the S i H4 gas, CH gas, and the gas to the gas inlet pipe 1.
008 into the deposition chamber 1001 through the gas discharge hole 1009. At this time, the SiH4 gas flow rate is 50SCC.
Mass flow controllers 1021 and 1023 were used to adjust the M, CH, and gas flow rates to 5003 CCM. While checking the vacuum gauge 1017, adjust the pressure inside the deposition chamber 1001 to 0.4 Torr by turning the main valve 101.
Adjusted the aperture of 6. Thereafter, the power of an RF power source (not shown) is set to 10 mW/cm', and RF power is introduced into the deposition chamber 1001 through the high frequency matching box 1012 to generate an RF glow discharge, and the third layer region of the upper layer is The formation of the fourth layer region is started, and when the fourth layer region of the upper layer with a layer thickness of 0.5 μm is formed, the RF glow discharge is stopped, and the outflow valves 1041 and 1043 and the auxiliary valve 1018 are closed. Then, the flow of gas into the deposition chamber 1001 was stopped, and the formation of the fourth layer region of the upper layer was completed.

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

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

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

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

The produced electrophotographic light-receiving members of Example 1 and Comparative Example were set in an electrophotographic apparatus that was a modified Canon NP-7550 copying machine for experimental purposes, and the electrophotographic light-receiving members were tested under various conditions. When we checked the electrophotographic characteristics of both, we found that both of them have an excellent effect on preventing interference fringes on images, especially when long wavelength light such as a semiconductor laser is used as the light source, and that extremely high quality images can be obtained. It was found that it has.

Next, we compared the number of spots as an image characteristic, and found that the diameter was 0. ], mm or less, it was found that the electrophotographic light-receiving member of Example 1 had a number of holes of 374 or less than the electrophotographic light-receiving member of Comparative Example.

Furthermore, in order to compare the degree of roughness, a diameter of 0.
The image density was measured at 100 points with a circular area of 0.5 mm in diameter as one unit, and the variation in image density was evaluated. The variation was 2/3 or less, and visual inspection also showed that the electrophotographic light-receiving member of Example 1 was superior to the electrophotographic light-receiving member of Comparative Example.

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 by changing the way the AlC1,/He gas flow rate changed in the lower layer, and the same evaluation was conducted. As a result, similar to Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

(Example 3) 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 the upper layer, H gas (not shown) was used as He gas (purity 99
．． 9999%) and SiF4 gas (not shown) (purity 9
9.999%) and N2 gas (purity 99.999%), an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 5, and the same evaluation was performed. However, similar to Example 1, good effects were obtained that improved the effects on creases, roughness, and layer peeling.

<Example 5> In the upper layer, H gas was replaced with Ar gas (not shown) (purity 99
．． 9999%), CH gas was changed to NH gas (not shown) (purity 99.999%), and an electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 6. As a result of various evaluations, similar to Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 6> In the upper layer, PH, /H, and gas (purity 99.
999%) was used to produce an electrophotographic light-receiving member in the same manner as in Example 1 under the production conditions shown in Table 7.
Similar evaluations were conducted, and as in Example 1, good effects were obtained in improving the edges, roughness, and layer peeling.

<Example 7> In Example 1, the NO gas cylinder was replaced with a S s Fa gas (purity 99.999%) cylinder, and S IF 4 and PH, /H gas (not shown) were further used in the upper layer. , An electrophotographic light-receiving member was prepared in the same manner as in Example 1 under the preparation conditions shown in Table 8, and the same evaluation was performed. As in Example 1, it was found that there were improvements in spotting, roughness, and layer peeling. Good effects were obtained.

<Example 8> PH, /H2 gas, and N2 gas (not shown) were further used in the upper layer, and Example 1 was prepared according to the production conditions shown in Table 9.
An electrophotographic light-receiving member was prepared in the same manner as in Example 1, and the same evaluation was performed. As in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 9> In Example 1, the CH4 gas cylinder was replaced with C2H.

Change to gas (purity 99.9999%) cylinder, change CH4 gas to C, H, gas in the upper layer, AlC1,
/He gas was further used to prepare an electrophotographic light-receiving member in the same manner as in Example 1 under the preparation conditions shown in Table 10, and the same evaluation was performed.
A good effect of improving roughness and layer peeling was obtained.

<Example 10> In the upper layer, B2H6 gas is heated to a pH (not shown).

/H, gas and under the production conditions shown in Table 11, an electrophotographic light receiving member was produced in the same manner as in Example 1, and the same evaluation was performed. A good effect on layer peeling was obtained.

<Example 11> In the upper layer, CH gas was changed to N Hs gas (not shown), SiH gas (not shown) (purity 99°999%) was further used, and Example 1 was carried out under the production conditions shown in Table 12. 1
An electrophotographic light-receiving member was prepared in the same manner as in Example 1, and the same evaluation was performed. As in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 12> The NO gas cylinder in Example 6 was changed to a SiF gas cylinder, S I Fa gas was further used in the upper layer, and the fabrication 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> PH, /H2 gas (not shown) in the upper layer.

An electrophotographic light-receiving member was prepared in the same manner as in Example 9 using S 12 Ha gas (purity 99.99%) and under the preparation conditions shown in Table 14, and the same evaluation was conducted. As in Example 9, good effects were obtained in improving 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> An electrophotographic light-receiving member was produced in the same manner as in Example 1 under the production conditions shown in Table 16, and the same evaluation was performed. A good effect was obtained that improved the results.

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

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

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

<Example 19> In Example 1, the outer diameter of the cylindrical aluminum support was set to 15 mm, and a light-receiving member for electrophotography was prepared in the same manner as in Example 1 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=25μm5b=0.8
An electrophotographic light-receiving member was prepared using a cylindrical aluminum-based support with a diameter of
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-8i (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 5xlO-'Torr.

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

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

After the preparation for film formation was completed as described above, the lower layer and the upper layer were formed on the cylindrical aluminum support 1107. To form the bottom layer, drain valve 1
041,1042.1047 and auxiliary valve 1018
Gradually open the SiHa gas, H2 gas, AlC1,
/He gas was flowed into the plasma generation region 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110.

At this time, the SiH gas flow rate was 1505 CCM.

H, gas flow rate is 20 S CCM 1A I C1a
/ Each mass flow controller 1021.1022.1027 so that the He gas flow rate is 4003 CCM.
Adjusted with. The pressure inside the deposition chamber 1ioi is 0.6 mTo
While checking a vacuum gauge (not shown), the opening of the main valve (not shown) was adjusted so that rr. After that, the power of the μW power supply (not shown) was set to 0.5 W/cm'', and the waveguide part 1
μW power was introduced into the plasma generation region 1109 through the dielectric window 1102 and the dielectric window 1102 to generate a μW glow discharge and start forming a lower layer on the cylindrical aluminum-based support 1107. During the formation of the bottom layer, the S I Ha gas flow rate is a constant flow rate of 1503 CCM, and the H2 gas flow rate is increased from 20 SCCM to 500 SCCM at a constant rate of AlCl.

/He gas flow rate is 400S at 0.01μm on the support side
SoscCM decreases at a constant rate from CCM to 80SCCM, and 50SC from soscCM at 0.01 μm on the upper layer side.
Adjust the mass flow controller 1021.1022.1027 so that the CM decreases at a constant rate, and the layer thickness is 0.
．． After forming a lower layer of 0.02 μm, the μW glow discharge is stopped, and the outflow valve 1041.1042.10
47 and the auxiliary valve 1018 were closed to stop the flow of gas into the plasma generation region 1109, and the formation of the lower layer was completed.

Next, to form the first layer region of the upper layer, the outflow valves 1041, 1042, 1044, 1045, 1046
and gradually open the auxiliary valve 1018 to supply 5iHa gas, H2 gas, G e Ha gas, B, H, /H, gas,
S iF a was flowed into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110 .

At this time, the SiH4 gas flow rate is 5008 CCMSH, the gas flow rate is 300 SCCM, the GeH gas flow rate is 11005 CCMSH, and the gas flow rate is 300 SCCM.
CC, B, H, /H, adjust with each mass flow controller 1021.1022.1024, 1025.1026 so that the gas flow rate is 1000 ppm relative to Si H4 gas and the SiFa gas flow rate is 2°SCCM. did. The pressure inside the deposition chamber 1101 is 0.4 mTor.
It was adjusted to be r.

After that, the μW main power supply power (not shown) is set to 0.5 W/cm3, and the μW main power supply power (not shown) is set to 0.5 W/cm3, 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 1 μm was formed.

Next, to form the second layer region of the upper layer, the outflow valves 1041, 1042, 1045, 1046 and the auxiliary valve 1018 are gradually opened to supply SiH4 gas, H2 gas, B, H6/H2 gas, S iF 4 gas was flowed into the plasma generation space 1109 through a gas discharge hole (not shown) of the gas introduction pipe 1110. At this time, the SiH4 gas flow rate is 5003CCM, H, the gas flow rate is 300SCCM, B
2H, /H, gas flow rate is 10 for S I H4 gas
00p1000pp<Gas flow rate is 203 CC? Each mass flow controller 1021.vf.
Adjusted with 1022, 1025.1026. Deposition chamber 11
The pressure inside 01 was adjusted to 0.4 mTorr. After that, the μW main power supply power (not shown) was increased to 0.5W/cm.
”, a μW glow discharge is generated in the plasma generation chamber 1109 in the same way as the lower layer, and the formation of the second layer region of the upper layer is started on the lower layer, and the second layer region of the upper layer with a layer thickness of 3 μm is generated. A layer region was formed.

Next, to form the third layer region of the upper layer, the outflow valves 1041, 1042, 1046 and the auxiliary valve 10
18 gradually open S I H4 gas, H2 gas, S
iF 4 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 7008 CCM, H gas flow rate is 500 SCCMSS iF a gas flow rate is 308 C
Each mass flow controller 10 to be CM
Adjusted with 21.1022.1026. Deposition chamber 1101
The internal pressure was adjusted to 0.5 mTorr.

After that, the μW main power supply power (not shown) is set to 0.5 W/cm", and the μW
A glow discharge was generated and the formation of the third layer region of the upper layer was started on the second layer region of the lower layer, thereby forming the third layer region of the upper layer with a layer thickness of 20 μm.

Next, to form the fourth layer region of the upper layer, the outflow valves 1041 and 1043 and the auxiliary valve 1018 are gradually opened to supply SiH4 gas, CH, and gas to the gas inlet pipe 111.
Plasma generation space 11 through gas discharge holes (not shown)
09. Each mass flow controller 1021.1 was adjusted so that the S t Ha gas flow rate was 150 SCCM and the CH4 gas flow rate was 5008 CCM.
Adjusted with 023. The pressure inside the deposition chamber 101 is 0.
The pressure was set at 3 mTorr. After that, the power of the μ~V power supply (not shown) is set to 0.5 W/cm", and the plasma generation chamber 1109
A .mu.W glow discharge was generated within the chamber to form a fourth layer region of the upper layer having a layer thickness of 1 .mu.m on the third 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> In Example 1, the CH4 gas cylinder was replaced with C=H2 gas (
A light-receiving member for electrophotography was prepared in the same manner as in Example 1 under the conditions shown in Table 23, except that CH4 gas was replaced with C and N2 gases in the upper layer. As a result of various evaluations, similar to Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 25> An electrophotographic light-receiving member was produced in the same manner as in Example 1 by changing the B=Ha/H-gas to PH,/H, gas (not shown) in the upper layer and using the production conditions shown in Table 24. make,
Similar evaluations were conducted, and as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 26> In Example 1, the No gas cylinder was changed to an NH gas cylinder, CH4 gas was changed to NHs gas in the upper layer, and S n H4 gas (not shown) was further used, and according to the production conditions shown in Table 25. A light-receiving member for electrophotography was prepared in the same manner as in Example 1, and the same evaluation was performed. As in Example 1, good effects were obtained in improving spots, roughness, and layer peeling. .

<Example 27> Further using SiF4 gas (not shown) in the upper layer,
An electrophotographic light-receiving member was produced in the same manner as in Example 6 under the production conditions shown in Table 26, and the same evaluation was performed. Good effects were obtained.

<Example 28> An electrophotographic light-receiving member was produced in the same manner as in Example 9 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> PH, /H, gas is further used in the upper layer, and the second
An electrophotographic light-receiving member was produced in the same manner as in Example 11 under the production conditions shown in Table 8, and the same evaluation was performed.
Similar to Example 11, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 30> In Example 1, 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 Fig. 39, with C=50 μm and d=
Using a cylindrical aluminum-based support with a thickness of 1 μm, changing the N2 gas to He gas (not shown) in the upper layer, and further using N2 gas (not shown), the fabrication conditions shown in Table 29 were the same as in Example 1. When a light receiving member for electrophotography was prepared and evaluated in the same way as in Example 1, both
A good effect of improving roughness and layer peeling was obtained.

<Example 31> A light-receiving member for electrophotography was produced in the same manner as in Example 1 under the production conditions shown in Table 30, further using A I C1s / He gas and SiFa gas (not shown) in the upper layer. However, similar evaluations were conducted, and as in Example 1, good effects were obtained in improving spots, roughness, and layer peeling.

<Example 32> AlCl,/He gas, N in the upper layer.

gas, SiFa gas (not shown) is further used, and a third
An electrophotographic light-receiving member was produced in the same manner as in Example 6 under the production conditions shown in Table 1, and the same evaluation was performed. As in Example 6, it was found to be improved against spots, roughness, and layer peeling. Good effects were obtained.

<Example 33> Electrophotography was performed in the same manner as in Example 1, except that the CH4 gas cylinder in Example 1 was changed to a C2'H2 gas cylinder, and the CH4 gas was changed to C, H, gas in the upper layer, and under the production conditions shown in Table 32. When a light-receiving member was prepared and evaluated in the same manner as in Example 1, it was found that, as in Example 1, good effects were obtained in terms of improvements in the areas of edges, roughness, and layer peeling.

<Example 34> In Example 1, the CH and gas cylinders were changed to C*' H2 gas cylinders, and the CH and gases were replaced with C and H2 in the upper layer.
Change the gas to B2H, /H, and replace the gas with PH, /H (not shown).
, gas, and under the production conditions shown in Table 33, an electrophotographic light-receiving member was produced in the same manner as in Example 1, and the same evaluation was performed. A good effect was obtained that improved the results.

゛〈Example 35〉 In the upper layer, AlC1,/He gas, Si (not shown)
F a , Hz S/He (purity 99.999%)
Using further gas, according to the preparation conditions shown in Table 34,
An electrophotographic light-receiving member was prepared in the same manner as in Example 6 and evaluated in the same manner as in Example 6. As in Example 6, good effects were obtained in improving spots, roughness, and layer peeling.

Table 1 Table 2 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8 Table 9 Table 10 Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 17 Table 18 Table 19 Table 20 Table 21 Table 22 Table 23 Table 24 Table 25 Table 26 Table 27 Table 28 Table 29 Table 30 Table 31 Table 32 Table 33 Table 34 [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 are solved. In particular, extremely excellent electrical properties, 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 (photovoltaic) between the aluminum support and the upper layer is formed. Injectability of the carrier) 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 spots are improved, and halftone It is possible to stably and repeatedly obtain high-quality images with clear images and high resolution.

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

In particular, by containing either germanium atoms or tin atoms in the layer region of the upper layer that is in contact with the lower layer, the adhesion between the upper layer and the lower layer is further improved, and the image This prevents defects and peeling of the Non-3i (H,X) film, and improves durability. Furthermore,
Even when long-wavelength light such as a semiconductor laser is used as a light source for the image exposure device of an electrophotographic device, the long-wavelength light that cannot be completely absorbed between the surface layer of the upper layer and the lower layer is absorbed with high efficiency. Therefore, the appearance of interference phenomena due to reflection of long wavelength light at the interface between the upper layer and the lower layer and/or the surface of the support can be significantly prevented, and the image quality can be dramatically improved.

[Brief explanation of 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 (A1) contained in the lower layer, and FIGS. 9 to 16, respectively.
The figures are explanatory diagrams of the distribution states of silicon atoms (Si) and hydrogen atoms (H) contained in the lower layer, respectively. ), carbon atom (C) and/or nitrogen atom (N) and/or oxygen atom (0), germanium atom (Ge) and/or tin atom (S n)
FIG. 37 is an explanatory diagram of the distribution state of RF.
A schematic explanatory diagram of a manufacturing device using a glow discharge method using
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. FIG. 40 is an enlarged view of the cross section of the support when the surface of the aluminum support is subjected to a so-called dimple treatment when forming the receiving member. FIG. 41 is a schematic explanatory diagram of a deposition apparatus when using a microwave glow discharge method. FIG. FIG. 2 is a schematic explanatory diagram of a manufacturing apparatus using a glow discharge method. Regarding FIG. 1, 100...Light receiving member for electrophotography of the present invention 101...
・Aluminum support 102...Pre-receiving layer 103...Lower layer 104...Upper layer 105...Regarding the free surface in FIG. 2, 200...Conventional light-receiving member for electrophotography 201...・
Aluminum support 202...Photosensitive layer 203 made of A-3i...Free surface In FIG. 37, 1000...Deposition device 1001 by RF glow discharge decomposition method...Deposition chamber 1005...Cylindrical Aluminum support 1008・
...Gas inlet pipe 1009...Gas discharge hole 1012...High frequency matching box 1014...
・Heating heater 1015...Leak valve 1016...Main valve 1017...Vacuum gauge 1018...Auxiliary valve] 020...Material gas supply device 1021-1027...Mass flow controller 1031-1037... Gas inflow valve 1041-1
047...Gas outflow valve 1051-1057...
Raw material gas cylinder knobs 1061 to 1067... Pressure regulators 1071 to 1077... Raw material gas cylinder 1078...
・Hermetically sealed container for raw materials In FIGS. 40 and 41, 1100...deposition device 1101 using microwave glow discharge method...deposition chamber 1102...dielectric window 1103...waveguide section 1107... Cylindrical aluminum support 1109
...Plasma generation area 1010...Gas introduction pipe No. 70 No. q side 80 Box 10th Figure 23 Figure 25 side 240 No. 26 C %387 3rd Wa section

Claims (1)

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