JPH0611875A - Electrophotographic light receptive member - Google Patents

Abstract

PURPOSE:To provide the electrophotographic light receptive member which has excellent electrical characteristics, image characteristics and durability and does not generate halftones, such as ghosts, particularly at the time of repetitive use at a high speed. CONSTITUTION:This light receptive member has a base body 101 and a light receptive layer laminated, successively from a base body side, with a first layer region 102 which is constituted of a non-single crystalline material contg. silicon atoms, germanium atoms, hydrogen atoms and/or halogen atoms as constituting elements and a second layer region 103 which is constituted of a non-single crystalline material consisting of silicon atoms as a base and contg. hydrogen atoms or/and halogen atoms as constituting elements and exhibits a photoconductivity on this base body. The content of the germanium atoms having at least one bond with the silicon atoms in the first layer region is 40 to 100% of the entire germanium atoms. The electrophotographic light receptive member having the excellent characteristics with which the 'ghosts' and unequal halftones are hardly observable, is obtd. while high electrostatic chargeability is maintained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electrophotography which is sensitive to electromagnetic waves such as light (in a broad sense, ultraviolet rays, visible rays, infrared rays, x-rays, γ-rays, etc.). The light receiving member for use.

The present invention also relates to a non-single-crystal light-receiving member having a silicon atom as a base, which is used in an electrophotographic image forming member, an image pickup device, a photoelectric conversion device, a solar cell and the like.

Particularly, it relates to improvement of the light receiving member.

[0004]

2. Description of the Related Art In the field of image formation, a photoconductive material for forming a light receiving layer in a light receiving member has high sensitivity,
The SN ratio [photocurrent (I _p ) / dark current (I _d )] is high, the absorption spectrum is adapted to the spectral characteristics of the electromagnetic wave irradiated, the photoresponsiveness is fast, and the desired dark resistance value is obtained. Characteristics such as being harmless to the human body when used are required. Particularly, in the case of an electrophotographic light receiving member incorporated in an electrophotographic apparatus used in an office as an office machine, the pollution-free property at the time of use is an important point.

Amorphous silicon (hereinafter referred to as "aS
i ”), for example, German publication No. 27469
No. 67, No. 2855718 and the like describe application as a light receiving member for electrophotography.

Further, Japanese Patent Laid-Open No. 58-171038 has a photoconductive amorphous layer made of an amorphous material containing silicon atoms and germanium atoms on a support. There is described a technique for increasing the photosensitivity in the entire visible light region by a photoconductive member having a non-uniform distribution state in the film thickness direction and being largely distributed on the support side, and particularly improving matching with a semiconductor laser.

Further, Japanese Patent Application Laid-Open No. 58-171039 discloses a first layer region made of an amorphous material containing silicon atoms and germanium atoms on a support, and an amorphous material containing silicon atoms. The light on the long wavelength side, which is not absorbed in the second layer region when a semiconductor laser is used, by the electrophotographic light-receiving member having the layer structure in which the second layer region having photoconductivity is provided. In the first layer region,
A technique for preventing interference due to reflected light from the support surface is described.

Further, in Japanese Patent Laid-Open No. 58-171046, an amorphous silicon germanium (hereinafter referred to as "a-SiGe") layer is made to contain an oxygen atom to obtain high dark resistance, high sensitivity, and adhesion. Japanese Patent Application Laid-Open No. 60-53957 discloses a technology for improving the dark resistance, sensitivity, and adhesion by adding nitrogen atoms to the a-SiGe layer.

These techniques have improved the electrical, optical and photoconductive properties of the electrophotographic light-receiving member using a-Si as a base material, and have also made it possible to improve the image quality.

[0010]

However, in recent years, electrophotographic copying machines are desired to have higher image quality, higher speed, and higher functions, and the electrophotographic light-receiving member is improved in overall electrical characteristics and image characteristics. The reality is that there is room for further improvement in achieving this.

In particular, for matching the light source with the semiconductor laser, and for effectively utilizing the light on the long wavelength side when used as a commonly used halogen lamp or fluorescent lamp light source, the long wavelength light of the light source is also used. In order to prevent the generation of interference fringes due to the reflected light from the support surface of a, the a-SiGe-based film has a layer structure having an a-SiGe layer region containing germanium atoms in the a-Si photoconductive layer. In the case where the afterimage, which is considered to be caused by the top of the photocarrier in the a-SiGe film, which is considered to be caused by the so-called "ghost" phenomenon and halftone unevenness, is caused by the repeated use at a high speed because the film quality has not been sufficiently improved. was there.

In electrophotographic copying machines, which have been desired to have higher image quality, higher speed, and higher functionality in recent years, the electrophotographic light-receiving member is further improved in electrical characteristics and photoconductive characteristics, and at the same time, halftone images such as photographs are provided. It is essential to be able to faithfully reproduce the included manuscript. Therefore, the photoreceptor for electrophotography is strongly desired to reduce the density unevenness of a halftone image, especially the ghost. In particular, in a full-color copying machine which has become widespread in recent years, the unevenness of the halftone image becomes a subtle unevenness of the color and becomes visually apparent, which is a serious problem.

Further, the prior art has shown conflicting effects with respect to the addition of metal as described above.

The present invention has been made in view of the above points, and has various problems in the light receiving member for electrophotography having the conventional light receiving layer composed of the material having the silicon atom as the base as described above. The purpose is to resolve.

That is, the main object of the present invention is that the electrical, optical and photoelectrical properties are substantially always stable with little dependence on the operating environment, and that they are excellent in light fatigue resistance.
Electrophotography that has a photoreceptive layer composed of a material with a silicon atom as the base material, which does not cause ghost or halftone unevenness even during repeated use at high speed, has excellent durability and moisture resistance, and has almost no residual potential observed. It is to provide a light receiving member for use.

[0016]

[Means for Solving the Problems]

(First Invention) The electrophotographic light-receiving member of the first invention is a non-single element containing a support and a silicon atom, a germanium atom, a hydrogen atom and / or a halogen atom on the support as constituent elements. A first layer region composed of a crystalline material,
A photoreceptive layer in which a second layer region composed of a non-single-crystal material containing silicon atoms as a host and hydrogen atoms and / or halogen atoms as constituents and exhibiting photoconductivity is sequentially laminated from the support side. Then, the germanium atom having at least one bond with a silicon atom in the first layer region is 40 to 1 of all germanium atoms in the first layer region.
It is characterized by being 00%.

The electrophotographic light-receiving member of the present invention designed to have the above-mentioned constitution can solve all of the above-mentioned problems, and has extremely excellent electric characteristics, optical characteristics and optical characteristics. Shows conductivity characteristics, image characteristics, and durability.

In order to solve the above-mentioned problems, in particular, image density unevenness such as ghost in a halftone image, the inventors of the present invention have earnestly studied to modify the layer region containing germanium in the photoconductive layer. I came. As a result, they have found that the object can be achieved by specifying the bonding state of germanium atoms in the layer region.

Hydrogenated amorphous silicon (hereinafter referred to as "a-Si (H,
X) ”), a film containing germanium atoms (hereinafter referred to as“ a-Si _1-x Ge _x
(H, X) ”), a-Si _1-x Ge _x
When the (H, X) film is formed without sticking to the bonding state as in the conventional case, the silicon atoms and the germanium atoms do not have a uniform distribution, and the high concentration portion of silicon atoms and the high concentration of germanium atoms are not formed. Therefore, the number of bonds between germanium atoms and silicon atoms (hereinafter referred to as “Ge—Si bond”) is less than the value expected from the composition. In such a film, for example, germanium atoms are expected to be incorporated as cluster-like lumps during the bonding of amorphous silicon atoms. When the bonding state of the constituent atoms in the film of the conventional silicon atom and germanium atom is analyzed by laser Raman spectroscopy in the a-SiGe system film, the germanium atom having at least one bond with the silicon atom is all in the film. It is as small as 30% or less of germanium atoms, and the bond between germanium atoms (hereinafter referred to as “G
It is found that the proportion of germanium atoms having “e-Ge bond”) is about 80% of all germanium atoms in the film. These facts indicate that a-SiGe (H,
X) This proves that germanium atoms form clusters in the film.

The influence of the clusters present in such an a-SiGe type film, which includes the imagination of the present inventors, is considered as follows.

First, the influence of a relatively large cluster can be considered. When forming an a-SiGe-based film, particularly when the content of germanium atoms is relatively large, it is considered that germanium atoms form large clusters in which several hundred germanium atoms are bonded to each other. If such large clusters are present in the film, carriers moving in the film may be easily trapped by the clusters.

It is also possible that the presence of relatively small clusters affects the stress of the a-SiGe film. For example, when there is a relatively small cluster in which germanium atoms are bonded to each other by several tens, the length of the bond of the silicon atom is different from that of the bond of the germanium atom, so that the cluster of the germanium atom and the silicon atom surrounding it. Stress will be generated during the binding of the. It is thought that the stress thus generated may worsen the running of the carrier.

From the above consideration, in particular, a-SiGe
In the system film, it is considered indispensable to improve the characteristics that the germanium atoms are evenly distributed in the silicon atoms to promote the Ge—Si bond and minimize the formation of germanium atom clusters. Therefore, the present inventors have made the proportion of germanium atoms having at least one Ge—Si bond at the time of controlling the bonding state in the formation of an a-SiGe-based film much larger than that of a conventional a-SiGe-based film. That is, all the problems mentioned above have been solved.

That is, according to the present invention, a-Si _1-x G
By improving the bonding state of the constituent atoms in the e _x (H, X) film, the optical memory is reduced and the "ghost" phenomenon and halftone unevenness are hardly seen while maintaining high chargeability. It was possible to obtain an electrophotographic light-receiving member having

Further in accordance with the present invention, a-Si _1-x Ge
The long-wavelength light absorption of the _x (H, X) film is significantly improved, and reflection from the substrate surface is performed with a smaller content of germanium atoms than the conventional a-Si _1-x Ge _x (H, X) film. It becomes possible to prevent interference due to light, and a-Si _1-x Ge _x
The cost reduction of the electrophotographic light-receiving member having the (H, X) film could be promoted.

Hereinafter, the electrophotographic light-receiving member of the present invention will be described in more detail with reference to the drawings.

FIG. 1 is a schematic sectional view showing an example of the layer structure of the electrophotographic light-receiving member of the present invention. The electrophotographic light-receiving member 100 of the present invention comprises a support 101 for a light-receiving member, and a first region 102, a- formed of a-Si _1-x Ge _x (H, X) on a support 101. The second region 103 made of Si (H, X) is sequentially laminated.

The support 101 used in the present invention is, for example, Al, Cr, Mo, Au, In, N.
Examples thereof include metals such as b, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. In addition, polyester, polyethylene, polycarbonate,
Also used is a support in which at least the surface of the electrically insulating support of the synthetic resin film or sheet such as cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, etc., on which the light receiving layer is formed, is electrically conductive, such as glass or ceramic. be able to. Furthermore, it is more preferable that the surface on the side opposite to the side on which the first layer region 102 is formed is also subjected to a conductive treatment.

Conductive support 1 used in the present invention
The shape of 01 may be a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface, and its thickness is appropriately determined so that the desired electrophotographic light-receiving member 100 can be formed. When flexibility as the electrophotographic light-receiving member 100 is required, it can be made as thin as possible within a range in which the function as the conductive support 101 can be sufficiently exhibited. However, the conductive support 101 is usually 1 in terms of mechanical strength in terms of manufacturing and handling.
It is set to 0 μm or more.

In particular, when image recording is performed using coherent light such as laser light, the conductive support 101 is used in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in visible images. You may provide unevenness on the surface of.

The unevenness provided on the surface of the conductive support 101 is described in JP-A-60-168156 and 60-17.
It is prepared by a known method described in JP-B-8457, JP-A-60-225854 and the like.

Further, as another method for more effectively eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, the surface of the conductive support 101 is uneven due to a plurality of spherical trace dents. A shape may be provided. That is, the surface of the conductive support 101 is the electrophotographic light receiving member 100.
Has unevenness smaller than the resolving power required for, and the unevenness is due to a plurality of spherical trace depressions. The unevenness due to the plurality of spherical trace depressions provided on the surface of the conductive support 101 is formed by a known method described in JP-A-61-235661.

The first layer region 102 of the present invention is made of a non-single-crystal material containing silicon atoms, germanium atoms, and hydrogen atoms as constituent elements, and the germanium atoms having at least one bond with silicon atoms are the first. It is formed so as to be 40 to 100% of all germanium atoms in one layer region.

The forming method is a plasma CVD method or a sputter vacuum deposition film forming method, in which numerical conditions of film forming parameters are appropriately set so that desired characteristics can be obtained. Specifically, for example, a glow discharge method, an ion plating method, or the like is preferable, but in any method, a germanium atom having a Ge—Si bond is included with respect to all germanium atoms contained in the first layer region. It is necessary to control the reaction so that the ratio is higher than that of the conventional a-SiGe based film.

In the case of the plasma CVD method such as the high frequency discharge method or the microwave discharge method, as an example of the method of controlling the binding of germanium atoms, the selection of the source gas species and the use of ions by applying an electric field during discharge Is mentioned.

In the first layer region, the total germanium source
Of germanium atom with Ge-Si bond to the child
As a method of increasing the content of S as a source gas, S
iH _Four , Si₂ H₆ And other silicon hydrides and SiHCl₃ etc
Chlorinated silicons and SiF _Four Such as silicon fluorides
Recon atom containing gas and raw material for supplying germanium atoms
GeHCl as gas₃ , GeH₂ Cl₂ , GeH₃ C
Relatively slow decomposition of hydrogenated germanium chloride such as l
It is especially important to use high-pressure gas
Effective in the case of law. Gas for supplying germanium
Together with the above hydrogenated germanium chloride-based gas, G
eH_Four , GeF_Four Etc. may be used. In addition, these
Raw gas for supplying recon atoms and germanium
Supply gas H as needed₂ , He, Ar, Ne, etc.
It may be diluted with a gas before use.

In the microwave discharge method, the effect of controlling the bonding state of germanium atoms is further enhanced by applying an electric field in the discharge space to effectively cause the ions to reach the surface of the support, in addition to the above method. become. This external electric bias may be a DC voltage, a pulsed voltage, a pulsating voltage whose magnitude changes with time rectified by a rectifier, or an AC voltage having a waveform such as a sine wave or a rectangular wave can be used. The voltage of the external electric bias is effective value of 15 V or more and 300 V or less, preferably 30 V
V or more and 200 V or less is suitable, but is appropriately determined in relation to other parameters so as to obtain desired characteristics of the deposited film.

The first region 102 of the light receiving member of the present invention.
Is preferably 40 to 40 in the ratio of germanium atoms having at least one Ge-Si bond to all germanium atoms contained in the a-Si _1-x Ge _x (H, X) film.
More preferably 100%, more preferably 45-100%, optimally 50
It is desirable to be 100%.

The content of germanium atoms in the first layer region of the present invention is preferably 20 to 80 atom% with respect to the sum of silicon atoms and germanium atoms, and more preferably 2
5 to 75 atom%, optimally 30 to 70 atom%, can be mentioned as desirable. This germanium atom is the first
Layer region may be uniformly contained in the photoconductive layer, or there may be a part having an uneven distribution such that the content varies in the layer thickness direction of the first layer region. . When the content of germanium atoms is less than 20% of the sum of silicon atoms and germanium atoms, the absorption of long-wavelength light from the light source is not sufficient, and the occurrence of halftone unevenness such as interference fringes is effectively prevented. Things get difficult. When the content of germanium atoms exceeds 80% of the sum of silicon atoms and germanium atoms, a-Si _1-x
At least 1 Ge—Si bond in the Ge _x (H, X) film
Even if the ratio of the germanium atoms possessed by the carrier is controlled to be higher than in the past, it becomes difficult for the carriers to travel, and the problems described above occur, especially the problem that image density unevenness such as ghost in halftone images easily occurs. Because
The effects of the present invention cannot be fully exerted.

In the present invention, the first layer region 102 is also used.
It is necessary that hydrogen atoms and / or halogen atoms are contained in it, which compensates for dangling bonds of silicon atoms and germanium atoms and improves the layer quality, especially photoconductivity and charge retention characteristics. This is because it is indispensable for making it happen. Therefore, the content of hydrogen atoms and / or halogen atoms is desirably 1 to 40 atom%, more preferably 3 to 35 atom%, and most preferably 5 to 30 atom%.

The amount of hydrogen atoms and / or halogen atoms contained in the first layer region 102 can be controlled by, for example, the temperature of the support 101, the inclusion of hydrogen atoms and / or halogen atoms. The amount of the raw material substance to be introduced into the reaction vessel, the discharge power, etc. may be controlled.

As the raw material gas for supplying the halogen atom used in the present invention, for example, a halogen gas, a halide, an interhalogen compound containing halogen,
Preference is given to gaseous or gasifiable halogen compounds such as halogen-substituted silane derivatives. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one. Halogen compounds that can be preferably used in the present invention include fluorine gas (F ₂ ), BrF, and Cl.
F, can be mentioned _{ClF 3, BrF 3, BrF 5} , lF 3, lF interhalogen compounds such as _7. Specific examples of the silicon compound containing a halogen atom, that is, a silane derivative substituted with a halogen atom include, for example, SiF.
Silicon fluoride such as ₄ , Si ₂ F ₆ can be mentioned as a preferable example.

Further, in the present invention, the first layer region 10
It is preferable that 2 contains an atom (M) that controls conductivity, if necessary. The atom that controls conductivity is the first
May be contained in the layer region 102 in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction.

As the atom for controlling the conductivity, so-called impurities in the field of semiconductors can be cited, and an atom belonging to Group III of the periodic table (hereinafter abbreviated as "Group III atom") which gives p-type conductivity. Or an atom belonging to Group V of the periodic table (hereinafter abbreviated as “Group V atom”) that imparts n-type conductivity.

Specific examples of the group III atom include B
(Boron), Al (aluminum), Ga (gallium),
There are In (indium), Tl (thallium), etc., and B, Al, and Ga are particularly preferable. As a Group V atom,
Specifically, there are P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc., and P and As are particularly preferable.

The content of atoms (M) controlling the conductivity contained in the first region 102 is preferably 1 × 10 5.
^-3 to 1 x 10 ⁵ atomic ppm, more preferably 1 x 10 ^-2
~ 5 x 10 ⁴ atomic ppm, optimally 1 x 10 ^-1 to 1 x 1
0 ⁴ preferably are atomic ppm. In order to structurally introduce a conductivity-controlling atom, for example, a group III atom or a group V atom, a raw material for introducing a group III atom or a group V atom for introducing a group III atom during layer formation. The raw material may be introduced in a gas state into the reaction vessel together with another gas for forming the first layer region 102. No. III
As a raw material for introducing a group atom or a raw material for introducing a group V atom, a gaseous substance at room temperature and atmospheric pressure or at least a gas which can be easily gasified under the layer forming condition is adopted. desirable. Specifically, as a raw material for introducing such a group III atom, for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B
Borohydrides such as ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ ,
Examples thereof include boron halides such as BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃
, InCl ₃ , TlCl _{3 and the} like can also be mentioned.

The present invention as a raw material for introducing a group V atom
Is effectively used in introducing phosphorus atoms
Is PH₃ , P₂ H_Four Phosphorus hydride, PH, etc._Four I, PF
₃ , PF_Five , PCl₃ , PCl_Five , PBr₃ , PBr
_Five , PI₃ And the like. Besides this, A
sH₃ , AsF₃ , AsCl₃ , AsBr₃ , AsF
_Five , SbH₃ , SbF₃ , SbF_Five , SbCl₃ , Sb
Cl_Five , BiH₃ , BiCl ₃ , BiBr₃ And so on
The effective starting materials for introducing atoms are
it can. In addition, for the introduction of atoms that control their conductivity
If necessary, H₂ , He, Ar, Ne, etc.
You may use it after diluting it with a soot.

By appropriately setting the introduction amount of these atoms for controlling the conductivity, the first layer region 102 can also serve as a blocking layer for blocking the injection of charges from the support. In addition, the support 101 and the first layer region 10
A blocking layer may be separately provided between the two layers and / or between the first layer region 102 and the second layer region 103.

Further, in the first layer region 102 of the present invention,
0.1 to 10000 atoms p of at least one element selected from Group Ia, Group IIa, Group VIa, and Group VIII of the Periodic Table
You may contain about pm. The element is the photoconductive layer second
It may be uniformly distributed in the region 103, or may be contained in the second layer region 103 evenly, but in a state of being unevenly distributed in the layer thickness direction. There may be some parts.

As the group Ia atom, specifically, Li
(Lithium), Na (sodium), K (potassium) can be mentioned, and as the group IIa atom, Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium) can be mentioned. Etc. can be mentioned.

Specific examples of the Group VIa atoms include Cr (chromium), Mo (molybdenum) and W (tungsten), and the Group VIII atoms include:
Fe (iron), Co (cobalt), Ni (nickel), etc. can be mentioned.

A region where the content of germanium atoms changes so as to decrease toward the second region may be provided between the first region 102 and the second region 103 of the present invention. It is possible to further reduce the influence of interference due to the reflected light at the interface between the region and the second region.

Further, in the light receiving member of the present invention, at least an aluminum atom, a silicon atom, a germanium atom, on the support 101 side of the first layer region 102,
It is desirable to have a layer region containing hydrogen atoms and / or halogen atoms in a non-uniform distribution state in the layer thickness direction.

Furthermore, in the present invention, the first layer region 10
In addition to the above atoms, 2 may contain any other atom as long as it is in a trace amount (1 atom% or less).

The film thickness of the first layer region 102 of the present invention is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, and is preferably 30 A.
˜20 μm, more preferably 50 A to 15 μm, optimally 100 A to 10 μm.

In order to form the first layer region 102 having the characteristics that can achieve the object of the present invention, the conductive support 101 is formed.
It is necessary to appropriately set the temperature and the gas pressure in the reaction container as desired.

The optimum temperature range (Ts) of the support 101 is selected according to the layer design.
Preferably 20-500 ° C, more preferably 50-48
It is desirable that the temperature is 0 ° C, optimally 100 to 450 ° C.

The gas pressure in the reaction vessel is also appropriately selected in accordance with the layer design, but in the usual case, it is preferably 1 × 10 ^{−5 to} 100 Torr, more preferably ⁵ × 10 ^{−5 to} 100 Torr.
× 10 ^{-5 to} 30 Torr, optimally 1 × 10 ^{-4 to} 10T
orr.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the substrate temperature and the gas pressure for forming the first layer region, but the conditions are not usually independently determined separately. It is desirable to determine the optimum value on the basis of mutual and organic relationships so as to form a light receiving member having desired characteristics.

The first region 102 of the light receiving member of the present invention.
Is 40 to 100% of the germanium atoms having at least one Ge—Si bond with respect to all the germanium atoms contained in the a-Si _1-x Ge _x (H, X) film, It is needless to say that the characteristics can be obtained by solving the above-mentioned problems, and the forming method thereof may be any method, and is not limited to the above method.

The second layer region 103 of the present invention is formed by the vacuum deposition film forming method by appropriately setting the numerical conditions of film forming parameters so that desired characteristics can be obtained. Specifically, for example, glow discharge method (AC discharge CVD such as low frequency CVD method, high frequency CVD method or microwave CVD method)
Method, or DC discharge CVD method), sputtering method, vacuum deposition method, ion plating method, photo CVD method
Can be formed by various thin film deposition methods such as a thermal CVD method and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted 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 prepared. The glow discharge method, the sputtering method, and the ion plating method are preferable because it is relatively easy to control the conditions for producing a photoreceptive member having characteristics. These methods may be used together in the same system.
For example, in order to form the second layer region 103 by the glow discharge method, basically, a source gas for Si supply capable of supplying silicon atoms (Si) and a source gas for H supply capable of supplying hydrogen atoms (H). Of the raw material gas and the raw material gas for supplying X, which can supply halogen atoms (X), are introduced in a desired gas state into a reaction vessel whose inside can be decompressed, and a glow discharge is generated in the reaction vessel. Then, a layer made of a-Si (H, X) may be formed on the surface of a predetermined support which is installed at a predetermined position in advance.

Further, in the present invention, the second layer region 103
It is necessary that hydrogen atoms and / or halogen atoms are contained therein, and this is to compensate for dangling bonds of silicon atoms and improve the layer quality, especially the photoconductivity and the charge retention property. This is because it is essential. Therefore, the content of hydrogen atoms is preferably 1 to 40 atom%, more preferably 3 to 35 atom%, and most preferably 50 to 30 atom%.
Is preferred.

Materials that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ and Si _3.
Gas hydrides such as H ₈ and Si ₄ H ₁₀ or silicon hydrides (silanes) that can be gasified are mentioned as being effectively used. Further, they are easy to handle during layer formation, have good Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferable. In addition, these raw material gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, or Ne as needed before use.

In order to make it easier to control the introduction ratio of hydrogen atoms introduced into the second layer region 103 to be formed, hydrogen gas or a silicon compound containing hydrogen atoms is added to these gases. It is preferable to form a layer by appropriately mixing gases. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio.

In order to structurally introduce hydrogen atoms into the second layer region 103, in addition to the above, H ₂ or SiH ₄ ,
It is also possible to cause discharge by causing silicon hydride such as Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ and silicon or a silicon compound for supplying Si to coexist in the reaction vessel.

The halogen source used in the present invention
For example, a halogen gas is effective as a raw material gas for child supply.
Halogen between gases including halogen gas, halide, and halogen
Compound, halogen-substituted silane derivative, etc.
Or a halogen compound which can be gasified is preferably mentioned.
It Further, a silicon atom and a halogen atom are further composed.
Gaseous or gasifiable halogen source as a component
Silicon hydride compounds containing a child are also listed as effective ones.
You can Halogenation preferably used in the present invention
As the compound, specifically, fluorine gas (F₂ ), BrF,
ClF, ClF ₃ , BrF₃ , BrF_Five , IF₃ , IF
₇ Interhalogen compounds such as Halogen
Substituted with so-called halogen atom
The silane derivative thus prepared is, for example, S
iF_Four , Si₂ F₆ Silicon fluoride such as
Can be listed.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the second layer region 103, for example, the temperature of the conductive support 101, the inclusion of hydrogen atoms and / or halogen atoms, and the like. The amount of the raw material used to be introduced into the reaction vessel, discharge power, etc. may be controlled.

It is also effective that the second layer region contains carbon atoms and / or oxygen atoms and / or nitrogen atoms. The content of carbon atoms and / or oxygen atoms and / or nitrogen atoms is preferably 0.00001 to 50 atom%, more preferably 0, relative to the sum of silicon atoms and carbon atoms and / or oxygen atoms and / or nitrogen atoms. .01
-40 atom%, optimally 1-30 atom% is desirable. Carbon atom and / or oxygen atom and / or nitrogen atom,
It may be uniformly contained in the second layer region,
There may be a portion having an uneven distribution so that the content changes in the layer thickness direction of the photoconductive layer.

Further, in the present invention, the second layer region 1
It is preferable that the atom 03 contains an atom (M) for controlling conductivity, if necessary. Atoms for controlling conductivity may be contained in the second region 103 of the photoconductive layer in a uniformly distributed state, or may be contained in a nonuniformly distributed state in the layer thickness direction. There may be.

As the above-mentioned atoms for controlling the conductivity, so-called impurities in the field of semiconductors can be cited, and an atom belonging to Group III of the periodic table (hereinafter abbreviated as "Group III atom") which gives p-type conductivity. Or an atom belonging to Group V of the periodic table (hereinafter abbreviated as “Group V atom”) that imparts n-type conductivity.

Specific examples of the group III atom include B
(Boron), Al (aluminum), Ga (gallium),
There are In (indium), Tl (thallium), etc., and B, Al, and Ga are particularly preferable. As a Group V atom,
Specifically, there are P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc., and P and As are particularly preferable.

The content of atoms (M) controlling the conductivity contained in the second region 103 is preferably 1 × 10 5.
^{-3 to} 5 x 10 ⁴ atomic ppm, more preferably 1 x 10 ^-2
~ 1 x 10 ⁴ atomic ppm, optimally 1 x 10 ^{-1 to} 5 x 1
It is desirable that the content be 0 ³ atomic ppm. In order to structurally introduce a conductivity-controlling atom, for example, a group III atom or a group V atom, a raw material for introducing a group III atom or a group V atom for introducing a group III atom during layer formation. The raw material may be introduced into the reaction vessel in a gas state together with another gas for forming the second layer region 103. No. III
As a raw material for introducing a group atom or a raw material for introducing a group V atom, a gaseous substance at room temperature and atmospheric pressure or at least a gas which can be easily gasified under the layer forming condition is adopted. desirable. Specifically, as a raw material for introducing such a group III atom, for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B
Borohydrides such as ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ ,
Examples thereof include boron halides such as BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃
, InCl ₃ , TlCl _{3 and the} like can also be mentioned.

The present invention as a raw material for introducing a group V atom
Is effectively used in introducing phosphorus atoms
Is PH₃ , P₂ H_Four Phosphorus hydride, PH, etc._Four I, PF
₃ , PF_Five , PCl₃ , PCl_Five , PBr₃ , PBr
_Five , PI₃ And the like. Besides this, A
sH₃ , AsF₃ , AsCl₃ , AsBr₃ , AsF
_Five , SbH₃ , SbF₃ , SbF_Five , SbCl₃ , Sb
Cl_Five , BiH₃ , BiCl ₃ , BiBr₃ And so on
The effective starting materials for introducing atoms are
it can.

Further, these raw materials for atom introduction for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

Further, in the second layer region 103 of the present invention,
0.1 to 10000 atoms p of at least one element selected from Group Ia, Group IIa, Group VIa, and Group VII of the periodic table
You may contain about pm. The element is the first photoconductive layer
It may be uniformly distributed in the region 103, or may be contained in the second layer region 103 evenly, but in a state of being unevenly distributed in the layer thickness direction. There may be some parts.

As the group Ia atom, specifically, Li
(Lithium), Na (sodium), K (potassium) can be mentioned, and as the group IIa atom, Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium) can be mentioned. Etc. can be mentioned.

Specific examples of the group VIa atoms include Cr (chromium), Mo (molybdenum) and W (tungsten), and the group VIII atoms include:
Fe (iron), Co (cobalt), Ni (nickel), etc. can be mentioned.

In the present invention, the layer thickness of the second layer region 103 is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, and is preferably 1 to 80 μm, more preferably The thickness is preferably 2 to 50 μm, and most preferably 3 to 40 μm.

In order to form the second layer region 103 having the characteristics capable of achieving the object of the present invention, the conductive support 101 is used.
It is necessary to appropriately set the temperature and the gas pressure in the reaction container as desired.

The temperature (Ts) of the conductive support 101 is appropriately selected depending on the layer design, but in the usual case, it is preferably 20 to 500 ° C., more preferably 50.
It is desirable to set the temperature to 480 ° C, optimally 100 to 450 ° C.

Similarly, the gas pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, it is preferably 1 × 10 ^{−5 to} 100 Torr, preferably 5 × 1.
0 ^{-5 to} 30 Torr, optimally 1 x 10 ^{-4 to} 10 Torr
It is preferably r.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the substrate temperature and the gas pressure for forming the second layer region, but the conditions are not usually decided independently and separately. It is desirable to determine the optimum value on the basis of mutual and organic relationships so as to form a light receiving member having desired characteristics.

Further, in the electrophotographic light-receiving member of the present invention, it is effective to provide a surface layer on the second layer region 103, and desired characteristics as the electrophotographic light-receiving member, such as charge retention, The environment resistance and abrasion resistance are further improved.

As a method for forming the surface layer, RF plasma CVD method, microwave, plasma CVD method, sputtering method, ion plating method and the like are preferably mentioned.

For example, a surface layer made of a-SiC is
In order to form by the microwave plasma CVD method, a Si supply gas capable of supplying silicon atoms and a C supply gas capable of supplying carbon atoms (C) are basically desired in a reaction vessel whose inside can be depressurized. It is sufficient to form a layer of a-SiC on the conductive substrate 101 installed in advance at a predetermined position by introducing it in the gas state of (1) to cause glow discharge in the reaction vessel.

Materials that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ , and Si _3.
Gas hydrides such as H ₈ and Si ₄ H ₁₀ or silicon hydrides (silanes) that can be gasified are mentioned as being effectively used. Further, they are easy to handle during layer formation, have good Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferable. Further, any way no problem to be present invention used as diluted by these H ₂ as needed starting material gas for Si supply, the He, Ar, gas Ne or the like.

Can be a source gas for introducing carbon atoms (C)
The starting materials effectively used as materials are C and H.
A constituent atom, for example, a saturated hydrocarbon having 1 to 5 carbon atoms,
C2-C4 ethylene hydrocarbons, C2-C3 hydrocarbons
Cetylene hydrocarbons and the like can be mentioned. Specifically, saturation
As hydrocarbons, methane (CH_Four ), Ethane (C₂H₆
 ), Propane (C₃ H₈ ), N-butane (n-C_Four H
_Ten), Pentane (C_FiveH₁₂), As an ethylene hydrocarbon
For ethylene (C₂ H_Four ), Propylene (C ₃ H
₆ ), Butene-1 (C_Four H₈ ), Butene-2 (C_Four H
₈ ), Isobutylene (C_Four H₈ ), Penten (C_Five 
H_Ten), As acetylene hydrocarbons, acetylene
(C₂ H₂ ), Methylacetylene (C₃ H_Four ), Butin
(C_Four H₆ ) And the like. Besides this, CF_Four , CF
₃ , C₂ F₆ , C₃ F₈ , C_Four F₈ Fluorocarbon compound such as
The thing can also be used as C supply gas of this invention. Also, this
If necessary, H may be used as a raw material gas for C supply.₂ , He,
It is also possible to use it after diluting it with a gas such as Ar or Ne.
It is effective in the clear. In addition, Si (CH₃ )_Four , Si (C
₂ H_Five ) _Four Alkyl silicide such as
It can be effectively used in the present invention.

In addition, nitrogen (N ₂ ) and ammonia (NH
₃ ) and other elements containing nitrogen atoms, oxygen (O ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), dinitrogen oxide (N ₂
O), carbon monoxide (CO), carbon dioxide (CO ₂ ) and other oxygen atom-containing elements, germanium tetrafluoride (GeF ₄ ),
The present invention is similarly effective even if a fluorine compound such as nitrogen fluoride (NF ₃ ) or a mixed gas thereof is introduced at the same time when the surface layer is formed.

Further, in the present invention, in addition to the above-mentioned atoms, the surface layer may contain any other atom in a trace amount (1 atom% or less).

The above-mentioned raw material gases used in the present invention may be supplied from different supply sources (cylinders), or it is also possible to use a gas which is mixed in a predetermined concentration in advance. Is effective for.

When a-SiC is used as the surface layer in the present invention, the content of carbon atoms is preferably 20 to 90 atom%, more preferably 30 to 85 atom% with respect to the sum of silicon atoms and carbon atoms. It is desirable that the content be 40 to 80 atomic%.

The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms is preferably 10 to 70 atom% with respect to the sum of silicon atoms, carbon atoms, hydrogen atoms and / or halogen atoms. , More preferably 20 to 65 atom%, and most preferably 30 to 60 atom%.

Further, a region where the carbon atom content and the hydrogen atom and / or halogen atom content gradually change may be provided between the second layer region and the surface layer.

In the present invention, the thickness of the surface layer is preferably 0.01 to 30 μm, more preferably 0.0, from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
The thickness is preferably 5 to 20 μm, and most preferably 0.1 to 10 μm.

The conditions for forming the surface layer in the present invention are as follows:
Appropriately determined so that desired electrophotographic characteristics can be obtained.
You can For example, the substrate temperature is appropriately selected in the optimum range.
However, preferably 20 to 500 ° C., more preferably 50
~ 480 ° C, optimally 100-450 ° C
Good Also, the gas pressure in the reaction vessel can be selected as appropriate.
However, it is preferably 1 × 10^-Five~ 100 Torr
More preferably 5 × 10 ^-Five~ 30 Torr, optimally 1x
10^-FourIt is desirable to set it to 10 Torr.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the substrate temperature and the gas pressure for forming the surface layer, but the conditions are not usually independently determined separately, and desired values are not required. It is desirable to determine the optimum value based on the mutual and organic relationships to form a characteristic light-receiving member.

Further, the layer structure of the electrophotographic light-receiving member formed according to the present invention may have a layer structure other than the above-mentioned photoconductive layer and surface layer, if necessary, in order to obtain desired characteristics as the electrophotographic light-receiving member. It is also effective to provide an adhesion layer having desired characteristics, a lower and / or upper charge injection blocking layer, and the like.

The procedure of the method for forming the electrophotographic light-receiving member of the first aspect of the present invention will be described below.

FIG. 2 schematically shows an example of the entire structure of the deposited film forming apparatus by the high frequency plasma CVD method. An example of the procedure for forming a photoconductive layer using this apparatus will be described below.

A cylindrical substrate 211 is provided in a reaction vessel 2111.
2 is installed, and the inside of the reaction vessel 2111 is exhausted by an exhaust device (not shown) (for example, a vacuum pump). Then, the temperature of the base 2112 is set to 20 by the heater 2113 for heating the support.
The temperature is controlled to a predetermined temperature of ℃ to 500 ℃.

A source gas for forming a deposited film is supplied to the reaction vessel 211.
Gas cylinder valves 2231-22
36, it is confirmed that the leak valve 2117 of the reaction container is closed, and the inflow valves 2241 to 224
6, outflow valves 2251 to 2256, auxiliary valve 226
Make sure 0 is open, then first open main valve 2
118 is opened and the reaction vessel 2111 and the gas pipe 21 are opened.
Evacuate 16.

Next, the reading of the vacuum gauge 2119 is about 5 × 10 ^-6
When it becomes Torr, the auxiliary valve 2260 and the outflow valves 2251 to 2256 are closed.

After that, each gas is introduced from the gas cylinders 2221 to 2226 by opening the gas cylinder valves 2231 to 2236, and each gas pressure is adjusted to ² Kg / cm ² by the pressure regulators 2261 to 2266. Next, the inflow valve 22
41 to 2246 are gradually opened to introduce each gas into the mass flow controllers 2211 to 2216.

After the preparation for film formation is completed as described above, a photoconductive layer and a surface layer are formed on the substrate 2112.

When the base body 2112 has reached a predetermined temperature, the necessary ones of the outflow valves 2251 to 2256 and the auxiliary valve 2260 are gradually opened to open the gas cylinder 22.
A predetermined gas from 21 to 2226 is introduced into the reaction vessel 2111 via the gas introduction pipe 2114. Next, the mass flow controllers 2211 to 2216 are adjusted so that each raw material gas has a predetermined flow rate. At that time, while watching the vacuum gauge 2119, the main valve 2118 is adjusted so that the pressure inside the reaction vessel 2111 becomes a predetermined pressure of 1 Torr or less.
Adjust the opening of. When the internal pressure is stable, the high frequency power supply 2120 is set to a desired power, and the high frequency power is introduced into the reaction vessel 2111 through the high frequency matching box 2115 to cause glow discharge. The raw material gas introduced into the reaction vessel is decomposed by this discharge energy, and a predetermined photoconductive layer is formed on the substrate 2112.
After the desired film thickness is formed, the supply of high frequency power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a desired light-receiving layer having a multilayer structure is formed.

When forming each layer, all outflow valves other than the necessary gas were closed, and the above-mentioned gas species and valve operation were not changed according to the preparation conditions of each layer. Needless to say.

The procedure of forming the electrophotographic light-receiving member in the case of using the deposited film forming apparatus by the microwave plasma CVD method will be described. 3 (A) and 3 (B) are diagrams schematically showing a vertical cross section and a horizontal cross section of an example of a reaction vessel of a deposited film forming apparatus of a microwave plasma CVD method, and FIG. 4 is an overall configuration of the apparatus. It is the figure which showed typically.

First, a cylindrical conductive substrate 3005 that has been degreased and washed in advance is placed in the reaction vessel 3001, and the conductive substrate 3005 is rotated by the driving device 3010.
The inside of the reaction container 3001 is exhausted through an exhaust pipe 3004 by an exhaust device (not shown) (for example, a vacuum pump), and the pressure inside the reaction container 3001 is adjusted to 1 × 10 ⁻⁶ Torr or less. Then, the temperature of the conductive substrate 3005 is heated and maintained at a predetermined temperature of 20 ° C. to 500 ° C. by the substrate heating heater 3006.

A raw material gas for forming the light receiving member is supplied to the reaction vessel 3
The gas cylinder valve 4031 is used to make the gas flow into 001.
~ 4036, make sure that the reaction vessel leak valve (not shown) is closed, and inflow valves 4041-4
046, outflow valves 4051 to 4056, auxiliary valve 4
After confirming that 060 is opened, first, the main valve (not shown) is opened to evacuate the inside of the reaction container 3001 and the gas pipe 4017.

Next, the reading of the vacuum gauge (not shown) is about 5 × 10.
^{When the} pressure reaches ^-6 Torr, the auxiliary valve 4060 and the outflow valves 4051-4056 are closed.

Thereafter, each gas is introduced from the gas cylinders 4021 to 4036 by opening the valves 4031 to 4036,
2Kg of each gas pressure by pressure regulators 4061-4066
Adjust to / cm ² . Next, the inflow valves 4041-40
46 is gradually opened and each gas is introduced into the mass flow controllers 4011 to 4016.

After the preparation for film formation is completed as described above, the photoconductive layer and the surface layer are formed on the conductive substrate 3005.

When the conductive substrate 3005 reaches a predetermined temperature, necessary ones of the outflow valves 4051 to 4056 and the auxiliary valve 4060 are gradually opened, and a predetermined gas is supplied from the gas cylinders 4021 to 4026.
It is introduced into the discharge space 3006 in the reaction container 3001 via 12. Next, mass flow controllers 4011-4
By 016, each source gas is adjusted to have a predetermined flow rate. At that time, the pressure in the discharge space 3006 is 1 Tor.
The opening of the main valve (not shown) is adjusted while observing the vacuum gauge (not shown) so that the predetermined pressure is equal to or lower than r. After the pressure is stabilized, a desired voltage is applied from the power supply 3009 to the electrode 3008, for example, an external electric bias, and a microwave power supply (not shown) is used to apply a frequency of 2.
A microwave of 45 GHz is generated, a microwave power source (not shown) is set to a desired power, and a discharge space 3006 μW is generated through the waveguide 3003 and the microwave introduction window 3002.
Energy is introduced to generate a μW glow discharge.
In this way, a predetermined light receiving member is formed on the conductive substrate 3005. At this time, in order to make the layer formation uniform, the driving means 3010 is rotated at a desired rotation speed.

After the desired film thickness is formed, the supply of μW electric power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a desired light-receiving layer having a multilayer structure is formed.

When forming each layer, all the outflow valves other than the necessary gas were closed, and the above-mentioned gas species and valve operation were not changed according to the preparation conditions of each layer. Needless to say. (Second invention) The second invention will be described below.

The electrophotographic light-receiving member of the present invention comprises a support and a silicon atom, a germanium atom, an oxygen atom and / or a nitrogen atom, and a hydrogen atom and / or a halogen atom as constituent elements on the support. A first layer region made of a non-single-crystal material, and a second layer region made of a non-single-crystal material containing a silicon atom as a base and containing a hydrogen atom and / or a halogen atom as a constituent and exhibiting photoconductivity. And a photoreceptive layer sequentially laminated from the support side, and germanium atoms having at least one bond with a silicon atom in the first layer region are 40 to 40% of all germanium atoms in the first layer region. 100%, and in the case of containing oxygen atoms, the oxygen atoms having at least one bond with a silicon atom contain 20 to 100% of all the oxygen atoms in the first layer region and the nitrogen atoms. If is characterized in that at least one having a nitrogen atom bonded to silicon atoms from 20 to 100% of the total nitrogen atoms in the first layer region.

The electrophotographic light-receiving member of the present invention designed to have the above-mentioned constitution can solve all of the above-mentioned problems, and has extremely excellent electric characteristics, optical characteristics, and optical characteristics. Shows conductivity characteristics, image characteristics, and durability.

The inventors of the present invention have made extensive studies to improve the layer region containing germanium in the photoconductive layer in order to solve the above-mentioned problems, particularly image density unevenness such as ghost in a halftone image. I came. As a result, they have found that the object can be achieved by specifying the bonding state of germanium atoms in the layer region and further specifying the bonding state of oxygen atoms and / or nitrogen atoms.

Germanium is formed in the lower region of the photoconductive layer of an amorphous silicon (hereinafter referred to as “a-Si: H, X”) film containing silicon atoms as a matrix and at least hydrogen atoms and / or halogen atoms as constituent elements. A film containing atoms and oxygen atoms and / or nitrogen atoms (hereinafter referred to as "a-
Si _x Ge _y O _u N _v (H, X) ”), and
When a -Si _x Ge _y O _u N _v (H, X) film is formed without sticking to the bonding state as in the past, silicon atoms, germanium atoms, and oxygen atoms and / or nitrogen atoms have a uniform distribution. However, there are high-concentration portions of silicon atoms, germanium atoms, and oxygen atoms and / or nitrogen atoms, respectively, which are likely to be mixed.
Therefore, a bond between a germanium atom and a silicon atom (hereinafter referred to as "Ge-Si bond"), a bond between an oxygen atom and a silicon atom (hereinafter referred to as "O-Si bond"), a bond between a nitrogen atom and a silicon atom (hereinafter referred to as " (Denoted as "N-Si bond") is less than that expected from the composition. In such a film, for example, germanium atoms are expected to be incorporated as cluster-like lumps during the bonding of amorphous silicon atoms. Conventional _{a-Si x Ge y O u} N v (H, X) based film with a laser Raman spectroscopy, FT-IR, Auger, analysis of the binding state of the constituent atoms in the film by SIMS or the like, and the silicon atom The number of germanium atoms having at least one of the bonds is as small as 30% or less of the total germanium atoms in the film, and the proportion of germanium atoms having a bond between germanium atoms (hereinafter referred to as “Ge-Ge bond”) is , 80% of all germanium atoms in the film are found, and these facts indicate that a-Si _x Ge _y O _u N _v (H,
X) This proves that germanium atoms form clusters in the film. Such a-Si _x Ge _y O _u which same is true for binding and / or binding between the nitrogen atom and silicon atom between the oxygen atoms and silicon atoms
The influence of the clusters present in the N _v (H, X) film-based film includes the imagination of the present inventors, but is considered as follows, for example.

First, the influence of a relatively large cluster can be considered. When forming an a-SiGe-based film, particularly when the content of germanium atoms is relatively large, it is considered that germanium atoms form large clusters in which several hundred germanium atoms are bonded to each other. If such large clusters are present in the film, carriers moving in the film may be easily trapped by the clusters.

The influence of stress on the a-SiGe type film due to the presence of relatively small clusters is considered. For example, when there is a relatively small cluster in which germanium atoms are bonded to each other by several tens, the length of the bond of the silicon atom is different from that of the bond of the germanium atom, so that the cluster of the germanium atom and the silicon atom surrounding it. Stress will be generated during the binding of the. It is thought that the stress thus generated may worsen the running of the carrier. The same thing can be considered when there is a high concentration portion of oxygen atoms and / or nitrogen atoms.

From the above consideration, in particular, a-Si _x G
and germanium atoms in the silicon atoms in the _{e y O u N v (H} , X) based film, an oxygen atom or / and nitrogen atoms are uniformly distributed, Ge-Si bonds and, O-Si bonds or /
It is considered essential to improve the properties by promoting the N-Si bond and reducing the formation of germanium atom, oxygen atom and / or nitrogen atom clusters as much as possible.

Therefore, the present inventors have found that a-Si _x Ge _y O
_u N _v (H, X) -based film formation by controlling the bonding state, the proportion of germanium atoms having at least one Ge-Si bond, and the proportion of oxygen atoms having at least one O-Si bond and / or At least 1 N-Si bond
The ratio of nitrogen atoms possessed by the conventional a-Si _x G
_{e y O u N v (H} , X) by considerably more than based film, it was led to solve all the above problems.

That is, according to the present invention, a-Si _x Ge
_{y O u N v (H,} X) by which to improve the binding state of the constituent atoms in the film, also saw while maintaining high chargeability "ghost" phenomenon or a half-tone unevenness is almost entirely in the repeated use of a high-speed It was possible to obtain a light receiving member for electrophotography having excellent properties that cannot be obtained.

Further, according to the present invention, it is possible to reduce image defects such as white spots caused by uneven foreign matter on the surface of the support. This and _{a-Si x Ge y O u} N v (H, X) film germanium atoms in the, by the oxygen atoms and / or nitrogen atoms are uniformly distributed, from the uneven portion and other foreign matter from the support This is probably because it has an effect of suppressing the abnormal growth of the film.

Further in accordance with the present invention, a-Si _x Ge _{y
O u N v (H, X} ) is the optical absorption of the long wavelength light based film greatly improved, inclusion of conventional _{a-Si x Ge y O u} N v (H, X) series less germanium atoms than films It is possible to prevent the interference due to the reflected light from the base surface depending on the amount, and
It was possible to promote cost reduction of the electrophotographic light-receiving member having the i _x Ge _y O _u N _v (H, X) -based film.

Hereinafter, the electrophotographic light-receiving member of the present invention will be described in more detail with reference to the drawings.

FIG. 1 is a schematic sectional view showing an example of the layer structure of the electrophotographic light-receiving member of the present invention. The electrophotographic light-receiving member 100 of the present invention comprises a support 101 for a light-receiving member, and a-Si _x Ge _y O _u N _v (H, X).
And a second region 103 made of a-Si (H, X) are sequentially laminated.

The support 101 used in the present invention is, for example, Al, Cr, Mo, Au, In, N.
Examples thereof include metals such as b, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. In addition, polyester, polyethylene, polycarbonate,
Also used is a support in which at least the surface of the electrically insulating support of the synthetic resin film or sheet such as cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, etc., on which the light receiving layer is formed, is electrically conductive, such as glass or ceramic. be able to. Furthermore, it is more preferable that the surface on the side opposite to the side on which the first layer region 102 is formed is also subjected to a conductive treatment.

Conductive support 1 used in the present invention
The shape of 01 may be a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface, and its thickness is appropriately determined so that the desired electrophotographic light-receiving member 100 can be formed. When flexibility as the electrophotographic light-receiving member 100 is required, it can be made as thin as possible within a range in which the function as the conductive support 101 can be sufficiently exhibited. However, from the viewpoint of mechanical strength, etc., the conductive support 101 is usually 1 in terms of manufacturing and handling.
It is set to 0 μm or more.

In particular, when image recording is performed using coherent light such as laser light, the conductive support 101 is used in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in visible images. You may provide unevenness on the surface of.

The unevenness provided on the surface of the conductive support 101 is described in JP-A-60-168156 and 60-17.
It is prepared by a known method described in JP-B-8457, JP-A-60-225854 and the like.

Further, as another method for more effectively eliminating the image defect due to the interference fringe pattern when the coherent light such as the laser light is used, the surface of the conductive support 101 is made uneven by a plurality of spherical trace depressions. A shape may be provided. That is, the surface of the conductive support 101 is the electrophotographic light receiving member 100.
Has unevenness smaller than the resolving power required for, and the unevenness is due to a plurality of spherical trace depressions. The unevenness due to the plurality of spherical trace depressions provided on the surface of the conductive support 101 is formed by a known method described in JP-A-61-235661.

The first layer region 102 of the present invention is composed of a non-single crystal material containing silicon atoms, germanium atoms, oxygen atoms and / or nitrogen atoms, and hydrogen atoms and / or halogen atoms as constituent elements. , 40 to 100% of germanium atoms having at least one bond with a silicon atom in the first layer region, and in the case of containing an oxygen atom, an oxygen atom having at least one bond with a silicon atom is 2 of all oxygen atoms in the first layer region
In the case of containing 0 to 100% and nitrogen atoms, the nitrogen atoms having at least one bond with the silicon atom are formed to be 20 to 100% of all the nitrogen atoms in the first layer region.

The forming method is a plasma CVD method or a sputtering vacuum deposition film forming method, in which numerical conditions of film forming parameters are appropriately set so that desired characteristics can be obtained. Specifically, for example, a glow discharge method, an ion plating method, or the like is preferable, but any method has at least one Ge—Si bond with respect to all germanium atoms contained in the first layer region. Conventionally, the ratio of germanium atoms and the ratio of oxygen atoms having at least one O—Si bond to all oxygen atoms or / and the ratio of nitrogen atoms having at least one N—Si bond to all nitrogen atoms are A-Si _x Ge _y O _u N _v
It is necessary to control the reaction so that it is higher than that of the (H, X) -based film.

In the case of the plasma CVD method such as the high frequency discharge method or the microwave discharge method, as an example of the method of controlling the bond of silicon atom, germanium atom, oxygen atom and / or nitrogen atom, selection of source gas species and discharge The use of ions by the application of an electric field inside is mentioned.

In the first layer region, an all-germanium source
Germanium with at least one Ge-Si bond for the child
O-Si bond with respect to the ratio of the nitrogen atoms and all oxygen atoms.
Ratio and / or total oxygen atoms having at least one
Nitrogen having at least one N-Si bond for a nitrogen atom
As a method to increase the ratio of elementary atoms more than ever,
SiH as a source gas for atom supply_Four , Si₂ H₆ Etc.
Silicon hydrides and SiHCl₃ Chlorinated silicon such as S, S
iF_Four Silicon atom-containing gas such as silicon fluorides,
GeHCl as a source gas for supplying germanium atoms
₃ , GeH₂ Cl ₂ , GeH₃ Hydrogenated chloride gel such as Cl
Use a gas that decomposes relatively slowly, such as
O as a raw material gas for child supply₂ , O₃ , H₂ O, etc., nitrogen
N as a source gas for atom supply₂ , NH₃ Etc.
As a source gas that can simultaneously supply oxygen and nitrogen atoms
NO, NO₂ , N₂ O, N₂ O₃ , N₂ O_Four , N₂ O
_Five It is especially preferable to use high frequency discharge method or microwave discharge
Effective in the case of law. Gas for supplying germanium
Together with the above hydrogenated germanium chloride-based gas, G
eH_Four , GeF_Four Etc. may be used. In addition, these
Source gas for supplying recon atoms, for supplying germanium atoms
Gas, raw material gas for oxygen atom supply and nitrogen atom supply
The raw material gas of H₂ , He, Ar, Ne, etc.
It may be diluted with a gas before use.

As the raw material gas for supplying halogen atoms used in the present invention, for example, a halogen gas, a halide, an interhalogen compound containing halogen,
Preference is given to gaseous or gasifiable halogen compounds such as halogen-substituted silane derivatives. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one. Halogen compounds that can be preferably used in the present invention include fluorine gas (F ₂ ), BrF, and Cl.
F, ClF ₃ , BrF ₃ , BrF ₅ , 1F ₃ , 1F _{7 and} other halogen compounds such as interhalogen compounds, a silicon compound containing a halogen atom, a so-called halogen atom-substituted silane derivative, For example SiF
Preferred are silicon fluorides such as ₄ , Si ₂ F _{6 and the} like.

In the microwave discharge method, a binding state of germanium atoms, oxygen atoms and / or nitrogen atoms is obtained by applying an electric field in the discharge space and effectively causing the ions to reach the surface of the support in the microwave discharge method. The effect of control of becomes larger. This external electric bias may be a DC voltage, a pulsed voltage, a pulsating voltage whose magnitude changes with time rectified by a rectifier, or an AC voltage having a waveform such as a sine wave or a rectangular wave can be used. The external electric bias voltage is 15V in effective value.
The above value is 300 V or less, preferably 30 V or more and 200 V or less, but is appropriately determined in relation to other parameters so that desired characteristics of the deposited film can be obtained.

The first region of the light receiving member of the present invention is 102
_{Is, a-Si x Ge y O} u N v (H, X) with respect to the total germanium atoms contained in the film, the proportion of at least one having germanium atoms Ge-Si bond is preferably 40 to 100% , More preferably 45 to 100%, most preferably 50 to 100%.

At least 1 bond with the silicon atom
The proportion of oxygen atoms contained therein is preferably 20 to 100% of all the oxygen atoms in the first layer region. More preferably 25 to 10
It is desirable that it is 0%, optimally 30 to 100%.

At least one bond with the silicon atom is used.
The proportion of nitrogen atoms contained therein is preferably 20 to 100% of the total nitrogen atoms in the first layer region. More preferably 25 to 10
It is desirable that it is 0%, optimally 30 to 100%.

The content of germanium atoms in the first layer region of the present invention is preferably 20 to 80 atom%, more preferably 2% with respect to the sum of silicon atoms and germanium atoms.
5 to 75 atom%, optimally 30 to 70 atom%, can be mentioned as desirable. This germanium atom is the first
Layer region may be uniformly contained in the photoconductive layer, or may have a non-uniform distribution such that the content varies in the layer thickness direction of the first layer region. .

When the content of germanium atoms is less than 20% with respect to the sum of silicon atoms and germanium atoms, absorption of particularly long-wavelength light by the light source is not sufficient, and halftone image unevenness such as interference fringes occurs. It becomes difficult to prevent effectively. In the case where the content of germanium atoms exceeds 80% with respect to the sum of silicon atoms and germanium _{atoms, a-Si x Ge y O} u N v (H, X) at least one of Ge-Si bonds in the film Even if the ratio of the germanium atoms possessed by the carrier is controlled to be higher than in the past, it becomes difficult for the carriers to travel, and the problems described above occur, especially the problem that image density unevenness such as ghost in halftone images easily occurs. Therefore, the effect of the present invention cannot be sufficiently exerted.

The content of oxygen atoms is preferably 0.00001 to 50 atom%, more preferably 0.01 to 40 atom%, optimally the sum of silicon atom, germanium atom, oxygen atom and nitrogen atom. Is preferably 1 to 30 atomic%.

The content of nitrogen atom is preferably 0.00001 to 50 atom%, more preferably 0.01 to 40 atom%, optimally the sum of silicon atom, germanium atom, oxygen atom and nitrogen atom. Is preferably 1 to 30 atomic%.

The oxygen atoms and / or nitrogen atoms may be uniformly contained in the first layer region, or may be non-uniformly distributed so that the content varies in the layer thickness direction of the photoconductive layer. There may be a part that has. When changing the content of oxygen atoms and nitrogen atoms, it is preferable to take the above content in the most oxygen atom and / or nitrogen atom portion, and in the region with few oxygen atom and / or nitrogen atom, There is no problem even if there is a portion with a content smaller than the range.

In the present invention, the first layer region 102 is also used.
It is necessary that hydrogen atoms or / halogen atoms are contained therein, which compensates dangling bonds of silicon atoms and germanium atoms and improves the layer quality, especially the photoconductivity and the charge retention property. This is because it is indispensable for this. Therefore, the content of hydrogen atom or halogen atom, or the amount of the sum of hydrogen atom and halogen atom, is based on the sum of silicon atom, germanium atom, oxygen atom and / or nitrogen atom, hydrogen atom and / or halogen atom. Preferably 1 to 40 atomic%, more preferably 3 to 3
It is desirable that the content is 5 atom%, and optimally 5 to 30 atom%.

The amount of hydrogen atoms and / or halogen atoms contained in the first layer region 102 can be controlled by, for example, the temperature of the support 101, the inclusion of hydrogen atoms and / or halogen atoms. The amount of the raw material substance introduced into the reaction vessel, the discharge power, and the like may be controlled.

It is also effective to contain carbon atoms in the first layer region, and the effect of the present invention can be further promoted. The content of carbon atoms is preferably 0.00001 to the sum of silicon atoms, germanium atoms and carbon atoms.
50 atomic%, more preferably 0.01 to 40 atomic%,
Optimally, 1 to 30 atomic% is desirable. Carbon atom is first
May be uniformly contained in the layer region, or may have a non-uniform distribution such that the content changes in the layer thickness direction of the photoconductive layer.

Can be a source gas for introducing carbon atoms (C)
The starting materials effectively used as materials are C and H.
A constituent atom, for example, a saturated hydrocarbon having 1 to 5 carbon atoms,
C2-C4 ethylene hydrocarbons, C2-C3 hydrocarbons
Cetylene hydrocarbons and the like can be mentioned. Specifically, saturation
As hydrocarbons, methane (CH_Four ), Ethane (C₂H₆
 ), Propane (C₃ H₈ ), N-butane (n-C_Four H
_Ten), Pentane (C_FiveH₁₂), As an ethylene hydrocarbon
For ethylene (C₂ H_Four ), Propylene (C ₃ H
₆ ), Butene-1 (C_Four H₈ ), Butene-2 (C_Four H
₈ ), Isobutylene (C_Four H₈ ), Penten (C_Five 
H_Ten), As acetylene hydrocarbons, acetylene
(C₂ H₂ ), Methylacetylene (C₃ H_Four ), Butin
(C_Four H₆ ) And the like. Besides this, CF_Four , CF
₃ , C₂ F₆ , C₃ F₈ , C_Four F₈ Fluorocarbon compound such as
The thing can also be used as C supply gas of this invention. Also, this
If necessary, H may be used as a raw material gas for C supply.₂ , He,
The present invention can also be used by diluting with a gas such as Ar or Ne.
Is effective for. In addition, Si (CH₃ )_Four , Si (C₂ 
H_Five )_FourAlkyl silicides such as
It is also effective in the present invention to use.

Further, in the present invention, the first layer region 10
It is preferable that 2 contains an atom (M) that controls conductivity, if necessary. The atom that controls conductivity is the first
May be contained in the layer region 102 in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction.

As the atom for controlling the conductivity, a so-called impurity in the field of semiconductors can be mentioned, and an atom belonging to Group III of the periodic table (hereinafter abbreviated as “Group III atom”) which gives p-type conductivity. Or an atom belonging to Group V of the periodic table (hereinafter abbreviated as “Group V atom”) that imparts n-type conductivity.

Specific examples of the group III atom include B
(Boron), Al (aluminum), Ga (gallium),
There are In (indium), Tl (thallium), etc., and B, Al, and Ga are particularly preferable. As a Group V atom,
Specifically, there are P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc., and P and As are particularly preferable.

The content of the atoms (M) controlling the conductivity contained in the first region 102 is preferably 1 × 10 5.
^-3 to 1 x 10 ⁵ atomic ppm, more preferably 1 x 10 ^-2
~ 5 x 10 ⁴ atomic ppm, optimally 1 x 10 ^-1 to 1 x 1
0 ⁴ preferably are atomic ppm. In order to structurally introduce a conductivity-controlling atom, for example, a group III atom or a group V atom, a raw material for introducing a group III atom or a group V atom for introducing a group III atom during layer formation. The raw material may be introduced in a gas state into the reaction vessel together with another gas for forming the first layer region 102. No. III
As a raw material for introducing a group atom or a raw material for introducing a group V atom, a gaseous substance at room temperature and atmospheric pressure or at least a gas which can be easily gasified under the layer forming condition is adopted. desirable. Specifically, as a raw material for introducing such a group III atom, for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B
Borohydrides such as ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ ,
Examples thereof include boron halides such as BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃
, InCl ₃ , TlCl _{3 and the} like can also be mentioned.

The present invention as a raw material for introducing a Group V atom
Is effectively used in introducing phosphorus atoms
Is PH₃ , P₂ H_Four Phosphorus hydride, PH, etc._Four I, PF
₃ , PF_Five , PCl₃ , PCl_Five , PBr₃ , PBr
_Five , PI₃ And the like. Besides this, A
sH₃ , AsF₃ , AsCl₃ , AsBr₃ , AsF
_Five , SbH₃ , SbF₃ , SbF_Five , SbCl₃ , Sb
Cl_Five , BiH₃ , BiCl ₃ , BiBr₃ And so on
The effective starting materials for introducing atoms are
it can. In addition, for the introduction of atoms that control their conductivity
If necessary, H₂ , He, Ar, Ne, etc.
You may use it after diluting it with a soot.

By appropriately setting the introduction amount of the atoms for controlling the conductivity, the first layer region 102 can also serve as a blocking layer for blocking the injection of charges from the support. In addition, the support 101 and the first layer region 10
2 and / or the first layer region 102 and the second layer region 1
A blocking layer may be separately provided between 03.

Further, in the first layer region 102 of the present invention,
0.1 to 10000 atom pp of at least one element selected from Group Ia, Group IIa, Group VIa and Group VII of the periodic table
You may contain about m. The element may be uniformly distributed in the first region 103 of the photoconductive layer, or may be uniformly contained in the second layer region 103, but is not uniform in the layer thickness direction. There may be a portion that contains it in a uniformly distributed state.

As the group Ia atom, specifically, Li
(Lithium), Na (sodium), K (potassium) can be mentioned, and as the group IIa atom, Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium) can be mentioned. Etc. can be mentioned.

Specific examples of the Group VIa atom include Cr (chromium), Mo (molybdenum) and W (tungsten), and the Group VII atom includes
Fe (iron), Co (cobalt), Ni (nickel), etc. can be mentioned.

A region in which the content of germanium atom, oxygen atom and / or nitrogen atom changes between the first region 102 and the second region 103 of the present invention so as to decrease toward the second region. May be provided, and the germanium atom, oxygen atom and / or nitrogen atom may be changed at the same time, or may be changed individually. This makes it possible to further reduce the influence of interference due to reflected light at the interface between the first region and the second region.

Further, in the light receiving member of the present invention, at least an aluminum atom, a silicon atom, a germanium atom, on the support 101 side of the first layer region 102,
It is desirable to have a layer region containing oxygen atoms and / or nitrogen atoms, hydrogen atoms and / or halogen atoms in a non-uniform distribution state in the layer thickness direction.

Furthermore, in the present invention, the first layer region 10
In addition to the above atoms, 2 may contain any other atom as long as it is in a trace amount (1 atom% or less).

The film thickness of the first layer region 102 of the present invention is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, and is preferably 30A to
20 μm, more preferably 50 A to 15 μm, most preferably 100 A to 10 μm.

In order to form the first layer region 102 having characteristics capable of achieving the object of the present invention, the conductive support 101 is used.
It is necessary to appropriately set the temperature and the gas pressure in the reaction container as desired.

The optimum temperature range (Ts) of the support 101 is appropriately selected according to the layer design.
Preferably 20-500 ° C, more preferably 50-48
It is desirable that the temperature is 0 ° C, optimally 100 to 450 ° C.

Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, but in the usual case, it is preferably 1 × 10 ^{−5 to} 100 Torr, more preferably ⁵ × 10 ^{−5 to} 100 Torr.
× 10 ^{-5 to} 30 Torr, optimally 1 × 10 ^{-4 to} 10T
It is preferably orr.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the substrate temperature and the gas pressure for forming the first layer region, but the conditions are not usually independently determined separately. It is desirable to determine the optimum value on the basis of mutual and organic relationships so as to form a light receiving member having desired characteristics.

First Region 102 of the Photoreceptive Member of the Invention
_{Is, a-Si x Ge y O} u N v (H, X) in a film 40 to 100% of the Ge-Si ratio of coupling at least one having germanium atoms are all germanium atom, if and containing an oxygen atom Is 20 to 100% of all oxygen atoms in the first layer region having oxygen atoms having at least one bond with a silicon atom, and in the case of containing a nitrogen atom, a nitrogen atom having at least one bond with a silicon atom is If the first layer region is formed so as to be 20 to 100% of all nitrogen atoms, the characteristics solving the above-mentioned problems can be obtained, and the forming method may be any method. It goes without saying that the method is not limited to this.

The second layer region 103 of the present invention is formed by the vacuum deposition film forming method by appropriately setting the numerical conditions of film forming parameters so that desired characteristics can be obtained. Specifically, for example, glow discharge method (AC discharge CVD such as low frequency CVD method, high frequency CVD method or microwave CVD method)
Method, or DC discharge CVD method), sputtering method, vacuum deposition method, ion plating method, photo CVD method
Can be formed by various thin film deposition methods such as a thermal CVD method and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted 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 prepared. The glow discharge method, the sputtering method, and the ion plating method are preferable because it is relatively easy to control the conditions for producing a photoreceptive member having characteristics. These methods may be used together in the same system.
For example, in order to form the second layer region 103 by the glow discharge method, basically, a source gas for Si supply capable of supplying silicon atoms (Si) and a source gas for H supply capable of supplying hydrogen atoms (H). The raw material gas for supplying X and the raw material gas for supplying X, which can supply halogen atoms (X), are introduced in a desired gas state into a reaction vessel in which the inside can be decompressed, and a glow discharge is caused in the reaction vessel. A layer made of a-Si (H, X) may be formed on a predetermined support 101 which is installed at a predetermined position in advance.

Further, in the present invention, the second layer region 103
It is necessary that hydrogen atoms and / or halogen atoms are contained therein, and this is to compensate for dangling bonds of silicon atoms and improve the layer quality, especially the photoconductivity and the charge retention property. This is because it is essential. Therefore, the content of hydrogen atom or halogen atom, or the amount of the sum of hydrogen atom and halogen atom is 1 to 40 atom% with respect to the sum of silicon atom and hydrogen atom and / or halogen atom,
It is more preferably 3 to 35 atomic%, and most preferably 5 to 30 atomic%.

The substances that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ , and Si _3.
Gas hydrides such as H ₈ and Si ₄ H ₁₀ or silicon hydrides (silanes) that can be gasified are mentioned as being effectively used. Further, they are easy to handle during layer formation, have good Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferable. In addition, these raw material gases for supplying Si may be diluted with a gas such as H ₂ , He, Ar, or Ne as needed before use.

In order to more easily control the introduction ratio of hydrogen atoms introduced into the second layer region 103 to be formed, hydrogen gas or a silicon compound containing hydrogen atoms is added to these gases. It is preferable to form a layer by appropriately mixing gases. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio.

In order to structurally introduce hydrogen atoms into the second layer region 103, in addition to the above, H ₂ or SiH ₄ ,
It is also possible to cause discharge by causing silicon hydride such as Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ and silicon or a silicon compound for supplying Si to coexist in the reaction vessel.

The halogen source used in the present invention
For example, a halogen gas is effective as a raw material gas for child supply.
Halogen between gases including halogen gas, halide, and halogen
Compound, halogen-substituted silane derivative, etc.
Or a halogen compound which can be gasified is preferably mentioned.
It Further, a silicon atom and a halogen atom are further composed.
Gaseous or gasifiable halogen source as a component
Silicon hydride compounds containing a child are also listed as effective ones.
You can Halogenation preferably used in the present invention
As the compound, specifically, fluorine gas (F₂ ), BrF,
ClF, ClF ₃ , BrF₃ , BrF_Five , IF₃ , IF
₇ Interhalogen compounds such as Halogen
Substituted with so-called halogen atom
The silane derivative thus prepared is, for example, S
iF_Four , Si₂ F₆ Silicon fluoride such as
Can be listed.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the second layer region 103, for example, the temperature of the conductive support 101, the inclusion of hydrogen atoms and / or halogen atoms, and the like. The amount of the raw material used to be introduced into the reaction vessel, discharge power, etc. may be controlled.

It is also effective that the second layer region contains carbon atoms and / or oxygen atoms and / or nitrogen atoms. The content of carbon atoms and / or oxygen atoms and / or nitrogen atoms is preferably 0.00001 to 50 atom%, more preferably 0, relative to the sum of silicon atoms and carbon atoms and / or oxygen atoms and / or nitrogen atoms. .01
-40 atom%, optimally 1-30 atom% is desirable. Carbon atom and / or oxygen atom and / or nitrogen atom,
It may be uniformly contained in the second layer region,
There may be a portion having an uneven distribution so that the content changes in the layer thickness direction of the photoconductive layer.

Further, in the present invention, the second layer region 1
It is preferable that the atom 03 contains an atom (M) for controlling conductivity, if necessary. Atoms for controlling conductivity may be contained in the second region 103 of the photoconductive layer in a uniformly distributed state, or may be contained in a nonuniformly distributed state in the layer thickness direction. There may be.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors, which are atoms belonging to Group III of the periodic table (hereinafter abbreviated as “Group III atoms”) that give p-type conductivity. Or an atom belonging to Group V of the periodic table (hereinafter abbreviated as “Group V atom”) that imparts n-type conductivity.

Specific examples of the group III atom include B
(Boron), Al (aluminum), Ga (gallium),
There are In (indium), Tl (thallium), etc., and B, Al, and Ga are particularly preferable. As a Group V atom,
Specifically, there are P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), etc., and P and As are particularly preferable.

The content of atoms (M) controlling the conductivity contained in the second region 103 is preferably 1 × 10 5.
^{-3 to} 5 x 10 ⁴ atomic ppm, more preferably 1 x 10 ^-2
~ 1 x 10 ⁴ atomic ppm, optimally 1 x 10 ^{-1 to} 5 x 1
It is desirable that the content be 0 ³ atomic ppm. In order to structurally introduce a conductivity-controlling atom, for example, a group III atom or a group V atom, a raw material for introducing a group III atom or a group V atom for introducing a group III atom during layer formation. The raw material may be introduced into the reaction vessel in a gas state together with another gas for forming the second layer region 103. No. III
As a raw material for introducing a group atom or a raw material for introducing a group V atom, a gaseous substance at room temperature and atmospheric pressure or at least a gas which can be easily gasified under the layer forming condition is adopted. desirable. Specifically, as a raw material for introducing such a group III atom, for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B
Borohydrides such as ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ , BF ₃ ,
Examples thereof include boron halides such as BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃
, InCl ₃ , TlCl _{3 and the} like can also be mentioned.

The present invention as a raw material for introducing a Group V atom
Is effectively used in introducing phosphorus atoms
Is PH₃ , P₂ H_Four Phosphorus hydride, PH, etc._Four I, PF
₃ , PF_Five , PCl₃ , PCl_Five , PBr₃ , PBr
_Five , PI₃ And the like. Besides this, A
sH₃ , AsF₃ , AsCl₃ , AsBr₃ , AsF
_Five , SbH₃ , SbF₃ , SbF_Five , SbCl₃ , Sb
Cl_Five , BiH₃ , BiCl ₃ , BiBr₃ And so on
The effective starting materials for introducing atoms are
it can.

Further, these raw material substances for atom introduction for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

Further, in the second layer region 103 of the present invention,
0.1 to 10000 atoms p of at least one element selected from Group Ia, Group IIa, Group VIa, and Group VIII of the Periodic Table
You may contain about pm. The element is the photoconductive layer second
It may be uniformly distributed in the region 103, or may be contained in the second layer region 103 evenly, but in a state of being unevenly distributed in the layer thickness direction. There may be some parts.

As the group Ia atom, specifically, Li
(Lithium), Na (sodium), K (potassium) can be mentioned, and as the group IIa atom, Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium) can be mentioned. Etc. can be mentioned.

Specific examples of the group VIa atom include Cr (chromium), Mo (molybdenum) and W (tungsten), and the group VIII atoms include Fe (iron) and Co (cobalt), Ni (nickel)
Etc. can be mentioned.

In addition, in the present invention, it is possible to contain any other atom in the second layer region 103, in addition to the above atoms, as long as it is in a trace amount (1 atom% or less).

In the present invention, the layer thickness of the second layer region 103 is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economic effects, and is preferably 1 to 80 μm, more preferably The thickness is preferably 2 to 50 μm, and most preferably 3 to 40 μm.

In order to form the second layer region 103 having the characteristics capable of achieving the object of the present invention, the conductive support 101 is used.
It is necessary to appropriately set the temperature and the gas pressure in the reaction container as desired.

The temperature (Ts) of the conductive support 101 is appropriately selected according to the layer design, but in the usual case, it is preferably 20 to 500 ° C., more preferably 50.
It is desirable to set the temperature to 480 ° C, optimally 100 to 450 ° C.

Similarly, the gas pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, it is preferably 1 × 10 ^{−5 to} 100 Torr, more preferably ⁵ × 10 ^{−5 to} 100 Torr.
× 10 ^{-5 to} 30 Torr, optimally 1 × 10 ^{-4 to} 10T
It is preferably orr.

In the present invention, the above-mentioned ranges are mentioned as the desirable numerical ranges of the substrate temperature and the gas pressure for forming the second layer region, but the conditions are not usually independently determined separately. It is desirable to determine the optimum value on the basis of mutual and organic relationships so as to form a light receiving member having desired characteristics.

Further, in the electrophotographic light-receiving member of the present invention, it is effective to provide a surface layer on the second layer region 103, and desired characteristics as the electrophotographic light-receiving member, for example, charge retention, The environment resistance and abrasion resistance are further improved.

As a method for forming the surface layer, RF plasma CVD method, microwave, plasma CVD method, sputtering method, ion plating method and the like are preferable.

For example, in order to form a surface layer composed of a-SiC (H, X) by the microwave plasma CVD method, basically, a Si supply gas capable of supplying silicon atoms and carbon atoms (C). And a C supply gas capable of supplying C are introduced into a reaction vessel whose inside can be decompressed in a desired gas state, a glow discharge is generated in the reaction vessel, and a is placed on a support 101 installed in advance at a predetermined position. A layer made of —SiC (H, X) may be formed.

The substances that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ and Si _3.
Gas hydrides such as H ₈ and Si ₄ H ₁₀ or silicon hydrides (silanes) that can be gasified are mentioned as being effectively used. Further, they are easy to handle during layer formation, have good Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferable. Further, any way no problem to be present invention used as diluted by these H ₂ as needed starting material gas for Si supply, the He, Ar, gas Ne or the like.

Can be a source gas for introducing carbon atoms (C)
The starting materials effectively used as materials are C and H.
A constituent atom, for example, a saturated hydrocarbon having 1 to 5 carbon atoms,
C2-C4 ethylene hydrocarbons, C2-C3 hydrocarbons
Cetylene hydrocarbons and the like can be mentioned. Specifically, saturation
As hydrocarbons, methane (CH_Four ), Ethane (C₂H₆
 ), Propane (C₃ H₈ ), N-butane (n-C_Four H
_Ten), Pentane (C_FiveH₁₂), As an ethylene hydrocarbon
For ethylene (C₂ H_Four ), Propylene (C ₃ H
₆ ), Butene-1 (C_Four H₈ ), Butene-2 (C_Four H
₈ ), Isobutylene (C_Four H₈ ), Penten (C_Five 
H_Ten), As acetylene hydrocarbons, acetylene
(C₂ H₂ ), Methylacetylene (C₃ H_Four ), Butin
(C_Four H₆ ) And the like. Besides this, CF_Four , CF
₃ , C₂ F₆ , C₃ F₈ , C_Four F₈ Fluorocarbon compound such as
The thing can also be used as C supply gas of this invention. Also, this
If necessary, H may be used as a raw material gas for C supply.₂ , He,
It is also possible to use it after diluting it with a gas such as Ar or Ne.
It is effective in the clear. In addition, Si (CH₃ )_Four , Si (C
₂ H_Five ) _Four Alkyl silicide such as
It can be effectively used in the present invention.

Further, as the source gas for supplying the halogen atom, a gaseous or gasifiable halogen compound such as a halogen gas, a halide, an interhalogen compound containing a halogen or a silane derivative substituted with a halogen is preferably used. To be Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one. Specific examples of the halogen compound that can be preferably used in the present invention include fluorine gas (F ₂ ), BrF, ClF, ClF ₃ and BrF.
Examples thereof include interhalogen compounds such as ₃ , BrF ₅ , IF ₃ and IF ₇ . A silicon compound containing a halogen atom,
As a so-called silane derivative substituted with a halogen atom, silicon fluoride such as SiF ₄ and Si ₂ F ₆ can be specifically mentioned as a preferable example.

In addition, nitrogen (N ₂ ), ammonia (NH
₃ ) and other elements containing nitrogen atoms, oxygen (O ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), dinitrogen oxide (N ₂
O), carbon monoxide (CO), carbon dioxide (CO ₂ ) and other oxygen atom-containing elements, germanium tetrafluoride (GeF ₄ ),
The present invention is similarly effective even if a fluorine compound such as nitrogen fluoride (NF ₃ ) or a mixed gas thereof is introduced at the same time when the surface layer is formed. Further, in the present invention, in addition to the above atoms, the surface layer may contain any other atom as long as it is in a trace amount (1 atom% or less).

The above-mentioned raw material gases used in the present invention may be supplied from different supply sources (cylinders), or it is also possible to use a gas mixed in advance at a constant concentration. Is effective for.

When a-SiC is used as the surface layer in the present invention, the content of carbon atoms is preferably 20 to 90 atom%, more preferably 30 to 85 atom% with respect to the sum of silicon atoms and carbon atoms. It is desirable that the content be 40 to 80 atomic%.

The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms is preferably 10 to 70 atom% with respect to the sum of silicon atoms, carbon atoms and hydrogen atoms and / or halogen atoms. , More preferably 20 to 65 atom%, and most preferably 30 to 60 atom%.

Further, a region where the carbon atom content and the hydrogen atom and / or halogen atom content gradually change may be provided between the second layer region and the surface layer.

In the present invention, the thickness of the surface layer is preferably 0.01 to 30 μm, more preferably 0.0 to 30 μm from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
The thickness is preferably 5 to 20 μm, and most preferably 0.1 to 10 μm.

The conditions for forming the surface layer in the present invention are as follows:
Appropriately determined so that desired electrophotographic characteristics can be obtained.
You can For example, the substrate temperature is appropriately selected in the optimum range.
However, preferably 20 to 500 ° C., more preferably 50
~ 480 ° C, optimally 100-450 ° C
Good Also, the gas pressure in the reaction vessel can be selected as appropriate.
However, it is preferably 1 × 10^-Five~ 100 Torr
More preferably 5 × 10 ^-Five~ 30 Torr, optimally 1x
10^-FourIt is desirable to set it to 10 Torr.

In the present invention, the above-mentioned ranges are mentioned as the desirable numerical ranges of the substrate temperature and the gas pressure for forming the surface layer, but the conditions are not usually independently determined separately, and the desired values are not required. It is desirable to determine the optimum value based on the mutual and organic relationships to form a characteristic light-receiving member.

Further, the layer constitution of the electrophotographic light-receiving member formed according to the present invention is such that the first layer region and the second layer region may be formed as necessary in order to obtain desired characteristics as the electrophotographic light-receiving member. It is also effective to provide an adhesion layer having desired characteristics, a lower and / or upper charge injection blocking layer, and the like in addition to the layer region and the surface layer.

The procedure of the method for forming the electrophotographic light-receiving member of the present invention will be described below.

FIG. 2 schematically shows an example of the entire structure of the deposited film forming apparatus by the high frequency plasma CVD method. An example of the procedure for forming a photoconductive layer using this apparatus will be described below.

A cylindrical substrate 211 is placed in a reaction vessel 2111.
2 is installed, and the inside of the reaction vessel 2111 is exhausted by an exhaust device (not shown) (for example, a vacuum pump). Then, the temperature of the base 2112 is set to 20 by the heater 2113 for heating the support.
The temperature is controlled to a predetermined temperature of ℃ to 500 ℃.

A source gas for forming a deposited film is supplied to the reaction vessel 211.
Gas cylinder valves 2231-22
36, it is confirmed that the leak valve 2117 of the reaction container is closed, and the inflow valves 2241 to 224
6, outflow valves 2251 to 2256, auxiliary valve 226
Make sure 0 is open, then first open main valve 2
118 is opened and the reaction vessel 2111 and the gas pipe 21 are opened.
Evacuate 16.

Next, the reading of the vacuum gauge 2119 is about 5 × 10 ^-6
When it becomes Torr, the auxiliary valve 2260 and the outflow valves 2251 to 2256 are closed.

After that, each gas is introduced from the gas cylinders 2221 to 2226 by opening the gas cylinder valves 2231 to 2236, and each gas pressure is adjusted to ² Kg / cm ² by the pressure adjusters 2261 to 2266. Next, the inflow valve 22
41 to 2246 are gradually opened to introduce each gas into the mass flow controllers 2211 to 2216.

After the preparation for film formation is completed as described above, a photoconductive layer and a surface layer are formed on the substrate 2112.

When the base body 2112 has reached a predetermined temperature, the necessary ones of the outflow valves 2251 to 2256 and the auxiliary valve 2260 are gradually opened to open the gas cylinder 22.
A predetermined gas from 21 to 2226 is introduced into the reaction vessel 2111 via the gas introduction pipe 2114. Next, the mass flow controllers 2211 to 2216 are adjusted so that each raw material gas has a predetermined flow rate. At that time, while watching the vacuum gauge 2119, the main valve 2118 is adjusted so that the pressure inside the reaction vessel 2111 becomes a predetermined pressure of 1 Torr or less.
Adjust the opening of. When the internal pressure is stable, the high frequency power supply 2120 is set to a desired power, and the high frequency power is introduced into the reaction vessel 2111 through the high frequency matching box 2115 to cause glow discharge. The raw material gas introduced into the reaction vessel is decomposed by this discharge energy, and a predetermined photoconductive layer is formed on the substrate 2112.
After the desired film thickness is formed, the supply of high frequency power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a desired light-receiving layer having a multilayer structure is formed.

When forming each layer, all the outflow valves other than the necessary gas were closed, and the above-mentioned gas species and valve operation were not changed according to the conditions for making each layer. Needless to say.

A procedure for forming the electrophotographic light-receiving member in the case of using the deposited film forming apparatus by the microwave plasma CVD method will be described. 3 (A) and 3 (B) are diagrams schematically showing a vertical cross section and a horizontal cross section of an example of a reaction vessel of a deposited film forming apparatus of a microwave plasma CVD method, and FIG.
FIG. 3 is a diagram schematically showing the overall configuration of the same device.

First, a cylindrical conductive substrate 3005, which has been degreased and washed in advance, is placed in the reaction container 3001, and the conductive substrate 3005 is rotated by the drive unit 3010.
The inside of the reaction container 3001 is exhausted through an exhaust pipe 3004 by an exhaust device (not shown) (for example, a vacuum pump), and the pressure inside the reaction container 3001 is adjusted to 1 × 10 ⁻⁶ Torr or less. Then, the temperature of the conductive substrate 3005 is heated and maintained at a predetermined temperature of 20 ° C. to 500 ° C. by the substrate heating heater 3006.

A raw material gas for forming the light receiving member is supplied to the reaction vessel 3
The gas cylinder valve 4031 is used to make the gas flow into 001.
~ 4036, make sure that the reaction vessel leak valve (not shown) is closed, and inflow valves 4041-4
046, outflow valves 4051 to 4056, auxiliary valve 4
After confirming that 060 is opened, first, the main valve (not shown) is opened to evacuate the inside of the reaction container 3001 and the gas pipe 4017.

Next, the reading of the vacuum gauge (not shown) is about 5 × 10.
^{When the} pressure reaches ^-6 Torr, the auxiliary valve 4060 and the outflow valves 4051-4056 are closed.

Then, each gas is introduced from the gas cylinders 4021 to 4036 by opening the valves 4031 to 4036,
2Kg of each gas pressure by pressure regulators 4061-4066
Adjust to / cm ² . Next, the inflow valves 4041-40
46 is gradually opened and each gas is introduced into the mass flow controllers 4011 to 4016.

After the preparation for film formation is completed as described above, the photoconductive layer and the surface layer are formed on the conductive substrate 3005.

When the conductive substrate 3005 reaches a predetermined temperature, the necessary ones of the outflow valves 4051 to 4056 and the auxiliary valve 4060 are gradually opened, and a predetermined gas is supplied from the gas cylinders 4021 to 4026.
It is introduced into the discharge space 3006 in the reaction container 3001 via 12. Next, mass flow controllers 4011-4
By 016, each source gas is adjusted to have a predetermined flow rate. At that time, the pressure in the discharge space 3006 is 1 Tor.
The opening of the main valve (not shown) is adjusted while observing the vacuum gauge (not shown) so that the predetermined pressure is equal to or lower than r. After the pressure is stabilized, a desired voltage is applied from the power supply 3009 to the electrode 3008, for example, an external electric bias, and a microwave power supply (not shown) is used to apply a frequency of 2.
A microwave of 45 GHz is generated, a microwave power source (not shown) is set to a desired power, and μ is supplied to the discharge space 3006 through the waveguide 3003 and the microwave introduction window 3002.
W energy is introduced to cause μW glow discharge. In this way, a predetermined light receiving member is formed on the conductive substrate 3005. At this time, in order to make the layer formation uniform, the driving means 3010 is rotated at a desired rotation speed.

After the desired film thickness is formed, the supply of μW electric power is stopped, the outflow valve is closed to stop the gas flow into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a desired light-receiving layer having a multilayer structure is formed.

When forming each layer, all the outflow valves other than the necessary gas were closed, and the above-mentioned gas species and valve operation were not changed according to the preparation conditions of each layer. Needless to say.

[0230]

EXAMPLES The first aspect of the present invention will now be described in more detail with reference to examples, but the present invention is not limited to these.

Using the manufacturing apparatus shown in FIGS. 3A and 3B and FIG. 4, an electrophotographic light-receiving member (hereinafter referred to as a drum) is formed on an aluminum cylinder which is mirror-finished according to the preparation conditions shown in Table 1. did. 3 (A) and FIG.
Separately, using the same type of apparatus as in (B) and forming only the a-Si _1-x Ge _x (H, X) film in the first layer region on the cylinder of the same use (hereinafter referred to as a sample) I prepared it. The drum side is an electrophotographic device (Canon NP
9330 was modified for the purpose of this test, especially for high-speed and high-quality images, and electrophotographic characteristics such as ghost, halftone unevenness and charging ability were evaluated.

Ghost: A Ghost test chart made by Canon (part number: FY9-9040) had a reflection density of 1,
1. Place a black circle with a diameter of 5 mm on the front edge of the image on the platen, and overlay a Canon halftone chart on it. The difference between the reflection density of 5 mm and the reflection density of the halftone portion was measured.

Halftone unevenness: a diameter of 0.05 m on a copy image obtained when a Canon halftone chart (part number: FY9-9042) is placed on a platen and copied.
The image density at 100 points was measured with the circular area of m as one unit, and the variation in the image density was evaluated.

Charging ability: A drum was installed in an experimental apparatus, a high voltage of +6 kV was applied to a charger to perform corona charging, and the surface potential of the dark portion of the electrophotographic light-receiving member 100 was measured by a surface potential meter.

⊚ indicates “excellently good”, ◯ indicates “good”, Δ indicates “no problem in practical use”, and x indicates “problem in practical use”.

For the sample, a plurality of parts corresponding to the upper and lower parts of the image part are cut out, and if necessary, Auger, SIMS, RBS, PRD, FT-IR, laser Raman spectroscopy, hot melt hydrogen analysis, etc. The quantitative analysis of the silicon atom, germanium atom, and hydrogen atom contained in the film and the analysis of the bonding state were carried out, and the ratio of the silicon atom, the germanium atom and the germanium atom having a Ge—Si bond in the film was calculated.

The above evaluation results are shown in Table 2 and the analysis results are shown in Table 3.
Are shown respectively.

As shown in Table 2, excellent electrophotographic characteristics with little ghost and halftone unevenness were obtained. (Comparative Example 1) A drum and a sample were prepared by the same apparatus and method as in Example 1 except that the preparation conditions were changed as shown in Table 4 and subjected to the same evaluation. The evaluation is shown in Table 5 and the analysis result is shown in Table 6.

As can be seen from Table 5, it was found that various items were inferior to those of Example 1. (Example 2 (Comparative Example 2)) A plurality of drums and samples for analysis were prepared under the same conditions as in Example 1 except that the conditions for creating the first layer region were changed to several conditions shown in Table 7. did. These drums and samples were evaluated and analyzed in the same manner as in Example 1, and the results shown in Tables 8 and 9 were obtained.

From these results, it is possible to improve the characteristics by setting the ratio of germanium atoms having at least one Ge-Si bond to 40% or more with respect to the total germanium atoms contained in the first layer region. I understood. (Example 3 (Comparative Examples 3 and 4)) A plurality of drums and analysis samples were prepared under the same conditions as in Example 1 except that the conditions for creating the first layer region were changed to several conditions shown in Table 10. Prepared. These drums and samples were evaluated and analyzed in the same manner as in Example 1, and the results shown in Tables 11 and 12 were obtained.

From these results, it was found that the characteristics are improved by setting the content of germanium atoms in the first layer region to 20 to 80%. (Example 4) Except that the preparation conditions were changed as shown in Table 13,
A drum and a sample were prepared by the same device and method as in Example 1. When the thus obtained drum was evaluated in the same manner as in Experimental Example 1, good characteristics were obtained as in Example 1. (Embodiment 5) In the manufacturing apparatus shown in FIG. 2, the power supply frequency is set to 105 MHz only when forming the first layer region, and the power supply frequency is set to 13.6 MH when forming the second layer region and the surface layer.
Using the high frequency plasma CVD method with Z, a drum and a sample were prepared in the same manner as in Experimental Example 1 except that the preparation conditions were changed as shown in Table 14. The drum thus obtained was evaluated in the same manner as in Experimental Example 1.
Good characteristics were obtained as well. When the sample was analyzed in the same manner as in Experimental Example 1, the content of germanium atoms was 54.8 atomic% with respect to the sum of silicon atoms and germanium atoms, and germanium having at least one Ge—Si bond was included. The atomic percentage was 64.6%.

Hereinafter, the second invention will be described in more detail with reference to Examples, but the invention is not limited thereto. (Embodiment 6) An electrophotographic light-receiving member (hereinafter referred to as a drum) is formed on an aluminum cylinder which is mirror-finished according to the preparation conditions shown in Table 15 using the manufacturing apparatus shown in FIGS. 3 (A), 3 (B) and 4. Was formed. Also, FIGS. 3 (A) and (B)
And using the device of the same type, a-Si _x of the first layer region on the cylinder of the same specifications _{Ge y O u N v (H} , X) film only one formed (hereinafter sample and expressed) separately I prepared. The drum side is an electrophotographic device (Canon NP
9330 was set for a high-speed, high-quality image for this test), and electrophotographic characteristics such as ghost, uneven halftone, and charging ability were evaluated.

Ghost: A ghost test chart made by Canon (part number: FY9-9040) had a reflection density of 1,
1. Place a black circle with a diameter of 5 mm on the front edge of the image on the platen, and overlay a Canon halftone chart on it. The difference between the reflection density of 5 mm and the reflection density of the halftone portion was measured.

Halftone unevenness: a diameter of 0.05 m on a copy image obtained when a Canon halftone chart (part number: FY9-9042) is placed on a platen and copied.
The image density at 100 points was measured with the circular area of m as one unit, and the variation in the image density was evaluated.

White spot: a full black chart made by Canon (part number: FY9-9073) is placed on the platen and copied, and the diameter is 0.2 m within the same area of the copy image obtained.
White spots of m or less were evaluated.

Charging ability: A drum was installed in an experimental apparatus, a high voltage of +6 kV was applied to the charger to carry out corona charging, and the surface potential of the dark portion of the electrophotographic light-receiving member 100 was measured by a surface potential meter.

Regarding each of the above four items, ⊚ represents “excellently good”, ◯ represents “good”, Δ represents “no problem in practical use”, and x represents “problem in practical use”.

For the sample, a plurality of portions corresponding to the upper and lower portions of the image area are cut out, and if necessary, Auger, SIMS, RBS, PRD, FT-IR, laser Raman spectroscopy, heat melting method, etc. Quantitative analysis of silicon atom, germanium atom, oxygen atom, nitrogen atom, and hydrogen atom contained in, and bond state analysis are carried out, and silicon atom, germanium atom, oxygen atom, nitrogen atom, and Ge-Si bond in the film are included. Germanium atom, OS
The ratios of oxygen atoms having i-bonds and nitrogen atoms having N-Si bonds were calculated.

The above evaluation results are shown in Table 16 and the analysis results are shown in Table 17.

As can be seen in Table 16, especially ghosts,
Excellent electrophotographic characteristics with less halftone unevenness and white spots were obtained. (Comparative Example 5) Except that the preparation conditions were changed as shown in Table 18,
A drum and a sample were prepared by the same apparatus and method as in Example 6 and subjected to the same evaluation. The evaluation is shown in Table 19 and the analysis result is shown in Table 20.

As shown in Table 19, it was found that various items were inferior to those of Example 6. (Example 7) Except that the preparation conditions were changed as shown in Table 21,
A drum and a sample were prepared by the same apparatus and method as in Example 6 and subjected to the same evaluation. The evaluation is shown in Table 22 and the analysis result is shown in Table 23. (Comparative Example 6) Except that the preparation conditions were changed as shown in Table 24,
A drum and a sample were prepared by the same apparatus and method as in Example 6 and subjected to the same evaluation. The evaluation is shown in Table 25, and the analysis result is shown in Table 26.

As shown in Table 25, it was found that various items were inferior to those of Example 7. (Example 8) Except that the preparation conditions were changed as shown in Table 27,
A drum and a sample were prepared by the same apparatus and method as in Example 6 and subjected to the same evaluation. The evaluation is shown in Table 28 and the analysis result is shown in Table 29. (Comparative Example 7) Except that the preparation conditions were changed as shown in Table 30,
A drum and a sample were prepared by the same apparatus and method as in Example 6 and subjected to the same evaluation. The evaluation is shown in Table 31 and the analysis result is shown in Table 32.

As shown in Table 31, it was found that various items were inferior to those of Example 8. (Example 9 (Comparative Example 8)) A plurality of drums and analysis samples were prepared under the same conditions as in Example 6 except that the conditions for creating the first layer region were changed to several conditions shown in Table 33. did. These drums and samples were evaluated and analyzed in the same manner as in Example 6, and the results shown in Tables 34 and 35 were obtained.

From these results, the ratio of germanium atoms having at least one Ge--Si bond to the total germanium atoms contained in the first layer region is 40.
%, At least 1 O-Si bond to all oxygen atoms.
It has been found that the characteristics are improved by setting the ratio of oxygen atoms having 20% or more and the ratio of nitrogen atoms having at least one N—Si bond to 20% or more with respect to all nitrogen atoms. (Example 10 (Comparative Examples 9 and 10)) A plurality of drums and analysis samples were prepared under the same conditions as in Example 6 except that the conditions for forming the first layer region were changed to several conditions shown in Table 36. Prepared. Example 6 of these drums and samples
As a result of performing the same evaluation and analysis as in Table 37 and Table 38
The results shown in are obtained.

From these results, it was found that the characteristics were improved by setting the content of germanium atoms in the first layer region to 20 to 80%. (Example 11) A drum and a sample were prepared by the same apparatus and method as in Example 6 except that the preparation conditions were changed as shown in Table 39. When the drum thus obtained was evaluated in the same manner as in Experimental Example 6, the same good characteristics as in Example 6 were obtained. (Example 12) A drum and a drum were produced in the same manner as in Example 6 except that the production conditions were changed as shown in Table 40 using the high frequency plasma CVD method with the power supply frequency set to 13.56 MHz in the manufacturing apparatus shown in FIG. I made a sample. When the drum thus obtained was evaluated in the same manner as in Example 6, good characteristics were obtained as in Example 6. When the sample was analyzed in the same manner as in Example 6,
The content of germanium atoms is 55.7 atom% with respect to the sum of silicon atoms and germanium atoms, of which Ge-
The proportion of germanium atoms having at least one Si bond is 65.3%, and the content of oxygen atoms is 6.2% with respect to the sum of silicon atoms, germanium atoms, oxygen atoms and nitrogen atoms, and O-Si bonds among them. The proportion of oxygen atoms having at least one is 34.6%, and the content of nitrogen atoms is 6.1% with respect to the sum of silicon atoms, germanium atoms, oxygen atoms and nitrogen atoms, of which N-Si bonds are included. The proportion of nitrogen atoms having at least one nitrogen atom was 33.5%. (Embodiment 13) In the manufacturing apparatus shown in FIG. 2, the power supply frequency is 105 MHz only when the first layer region is formed, and the power supply frequency is 13.56 MHz when the charge injection blocking layer, the second layer region and the surface layer are formed. Drums and samples were produced in the same manner as in Example 6 except that the production conditions were changed as shown in Table 41 by using the high frequency plasma CVD method described above. When the drum thus obtained was evaluated in the same manner as in Example 6, good characteristics were obtained as in Example 6.
Further, when the sample of the first layer region was analyzed in the same manner as in Example 6, the content of germanium atoms was 56.1 atomic% with respect to the sum of silicon atoms and germanium atoms.
The proportion of germanium atoms having at least one Ge-Si bond is 67.7%, and the content of oxygen atoms is 6.5% with respect to the sum of silicon atoms, germanium atoms, oxygen atoms and nitrogen atoms. The proportion of oxygen atoms having at least one O—Si bond is 37.6%, and the content of nitrogen atoms is 6.2% with respect to the sum of silicon atoms, germanium atoms, oxygen atoms and nitrogen atoms. The proportion of nitrogen atoms having at least one N—Si bond was 36.9%.

[0256]

[Table 1]

[0257]

[Table 2]

[0258]

[Table 3]

[0259]

[Table 4]

[0260]

[Table 5]

[0261]

[Table 6]

[0262]

[Table 7]

[0263]

[Table 8]

[0264]

[Table 9]

[0265]

[Table 10]

[0266]

[Table 11]

[0267]

[Table 12]

[0268]

[Table 13]

[0269]

[Table 14]

[0270]

[Table 15]

[0271]

[Table 16]

[0272]

[Table 17]

[0273]

[Table 18]

[0274]

[Table 19]

[0275]

[Table 20]

[0276]

[Table 21]

[0277]

[Table 22]

[0278]

[Table 23]

[0279]

[Table 24]

[0280]

[Table 25]

[0281]

[Table 26]

[0282]

[Table 27]

[0283]

[Table 28]

[0284]

[Table 29]

[0285]

[Table 30]

[0286]

[Table 31]

[0287]

[Table 32]

[0288]

[Table 33]

[0289]

[Table 34]

[0290]

[Table 35]

[0291]

[Table 36]

[0292]

[Table 37]

[0293]

[Table 38]

[0294]

[Table 39]

[0295]

[Table 40]

[0296]

[Table 41]

[0297]

The electrophotographic light-receiving member of the present invention can solve the problems of the conventional electrophotographic light-receiving members.

That is, according to the first aspect of the present invention, in the a-Si _1-x Ge _x (H, X) film in the lower region of the photoconductive layer, Ge-Si is contained with respect to all contained germanium atoms.
The ratio of germanium having at least one bond is 40-
By setting the content to 100%, it is possible to obtain an electrophotographic light-receiving member having excellent characteristics in which "ghost" phenomenon and halftone unevenness are hardly observed while keeping high charging ability.

Further in accordance with the present invention, a-Si _1-x Ge
_Since the absorption of long-wavelength light in the _x (H, X) film is significantly improved, it becomes possible to reduce the content of germanium atoms as compared with the conventional a-Si _1-x Ge _x (H, X) film. a
It is possible to promote cost reduction of the electrophotographic light-receiving member having a —Si _1-x Ge _x (H, X) film.

According to the second aspect of the present invention, in the a-Si _1-x Ge _y O _u N _v (H, X) -based film in the lower region of the photoconductive layer, the total germanium atoms contained are , Ge
The proportion of germanium having at least one —Si bond is 40 to 100%, the proportion of oxygen atoms having at least one O—Si bond to all oxygen atoms is 20 to 100%, and / or N to all nitrogen atoms. -Si bond of at least 1
By setting the ratio of nitrogen atoms to be retained to 20 to 100%, "ghost" phenomenon and halftone unevenness are hardly observed while maintaining high chargeability even when repeatedly used at high speed, and image defects such as white spots. It is possible to obtain a photoreceptive member for electrophotography, which has excellent properties with less heat.

Further in accordance with the present invention, a-Si _1-x Ge
_{y O u N v (H,} X) the absorption of the long wavelength light based film is significantly improved, it is possible to reduce the content of germanium atoms _{Conventionally, a-Si 1-x Ge} y O u N _v
The cost reduction of the electrophotographic light-receiving member having the (H, X) -based film can be promoted.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing an example of a layer structure of a light receiving member for electrophotography of the present invention.

FIG. 2 is a schematic diagram showing an example of the entire configuration of a deposited film forming apparatus using a high frequency plasma CVD method.

3A and 3B are schematic views of an example of a reaction container of a deposited film forming apparatus by a microwave plasma CVD method, FIG. 3A is a vertical sectional view, and FIG. 3B is a horizontal sectional view.

FIG. 4 is an example of a schematic configuration diagram of the entire deposited film forming apparatus by a microwave plasma CVD method.

[Explanation of symbols]

 100 Electrophotographic Photoreceptive Member 101 Conductive Substrate 102 First Layer Region 103 Second Layer Region 2000 Deposition Device 2111 Reaction Container 2112 Substrate 2113 Substrate Heating Heater 2114 Raw Material Gas Introducing Pipe 2115 High Frequency Matching Box 2116 Gas Pipe 2117 Leak Valve 2118 Main valve 2119 Vacuum gauge 2120 High frequency power supply 2200 Gas supply device 2211 to 2216 Mass flow controller 2221 to 2226 Gas cylinder 2231 to 2236 Gas cylinder valve 2241 to 2246 Inflow valve 2251 to 2256 Outflow valve 2260 Auxiliary valve 2261 to 2266 Pressure regulator 3000 Deposited film Forming apparatus 3001 Reaction container 3002 Microwave introducing dielectric window 3003 Waveguide 3004 Exhaust pipe 3005 Conductivity Body 3006 Discharge space 3007 Heater 3008 Electrode 3009 Power supply 3010 Driving means (rotating motor) 3011 Holder 3012 Gas introduction pipe 4000 Raw material gas supply device 4011-4016 Mass flow controller 4017 Gas pipe 4021-4026 Gas cylinder 4031-4036 Gas cylinder valve 4041-4046 Inflow valve 4051-4056 Outflow valve 4060 Auxiliary valve 4061-4066 Pressure regulator

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji Obishi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (10)

[Claims] 1. A first substrate composed of a support and a non-single-crystal material containing silicon atoms, germanium atoms, hydrogen atoms and / or halogen atoms as constituent elements on the support.
Layer area and hydrogen atoms or
And a photoreceptive layer in which a second layer region composed of a non-single-crystal material containing a halogen atom as a constituent and exhibiting photoconductivity is sequentially laminated from the support side, and in the first layer region, A photoreceptive member for electrophotography, wherein the germanium atom having at least one bond with a silicon atom accounts for 40 to 100% of all germanium atoms in the first layer region. 2. The electrophotographic apparatus according to claim 1, wherein the content of germanium atoms in the first layer region is 20 to 80 atom% with respect to the sum of silicon atoms and germanium atoms. Light receiving member. 3. A region between the first layer region and the second layer region, the region having a germanium atom content decreasing toward the second layer region, or 1. The light-receiving member for electrophotography according to claim 2. 4. A surface layer formed of a non-single crystal material containing silicon atoms, carbon atoms, hydrogen atoms and / or halogen atoms as constituent elements on the photoconductive layer. The light-receiving member for electrophotography according to claim 1. 5. A non-single crystal material comprising a support and a silicon atom, a germanium atom, a hydrogen atom, an oxygen atom and / or a nitrogen atom, and a hydrogen atom and / or a halogen atom as constituent elements on the support. A first layer region formed and a second layer region which is made of a non-single crystal material containing silicon atoms as a host and hydrogen atoms and / or halogen atoms as constituents and which exhibits photoconductivity, are provided from the support side. And a photoreceptive layer sequentially stacked, and the germanium atom having at least one bond with a silicon atom in the first layer region is 40% of all germanium atoms in the first layer region.
˜100% and oxygen atoms having at least one bond with silicon atoms in the case of containing oxygen atoms are 20 to 100% of all oxygen atoms in the first layer region and silicon atoms in the case of containing nitrogen atoms. Is a nitrogen atom having at least one bond of 20 to 100% of all nitrogen atoms in the first layer region. 6. The electrophotographic apparatus according to claim 5, wherein the content of germanium atoms in the first layer region is 20 to 80 atom% with respect to the sum of silicon atoms and germanium atoms. Light receiving member. 7. In the first layer region, the content of oxygen atoms is 0.00001 to 50% with respect to the sum of silicon atoms, germanium atoms, oxygen atoms and nitrogen atoms, and the content of nitrogen atoms is 0.0000 for the sum of silicon atom, germanium atom, oxygen atom and nitrogen atom
The light receiving member for electrophotography according to claim 5 or 6, wherein the content is 1 to 50 atom%. 8. The content of hydrogen atoms and / or halogen atoms in the first layer region is 1 to the sum of silicon atoms, germanium atoms, oxygen atoms and nitrogen atoms, and hydrogen atoms and halogen atoms. The light receiving member for electrophotography according to claim 5, wherein the content is 40 atom%. 9. A region between the first layer region and the second layer region, the region in which the content of germanium atoms, oxygen atoms and / or nitrogen atoms decreases toward the second layer region. 9. The light receiving member for electrophotography according to claim 5, wherein the light receiving member is for electrophotography. 10. A surface layer made of a non-single-crystal material containing silicon atoms, carbon atoms, hydrogen atoms and / or halogen atoms as constituent elements on the second layer region. The light receiving member for electrophotography according to claim 5.