JP3154259B2 - Light receiving member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a photoreceptor which is sensitive to electromagnetic waves such as light (here, light in a broad sense, meaning ultraviolet, visible, infrared, X-ray, gamma-ray, etc.). Regarding members.

[0002]

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.
A high SN ratio [photocurrent (I _D ) / dark current (I _d )], having an absorption spectrum suitable for the spectral characteristics of the electromagnetic wave to be radiated, fast photoresponse, and a desired dark resistance value; Harmless to human body when used,
And other characteristics are required. In particular, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used in an office as an office machine, the above-described non-polluting property at the time of use is important.

Based on such a point, amorphous silicon (hereinafter referred to as “a-S
i "), for example, German Patent Application Publication No. 2
No. 7,469,674 and No. 2,855,718 describe applications as light receiving members for electrophotography.

FIG. 3 shows a conventional light receiving member 20 for electrophotography.
FIG. 2 is a cross-sectional view schematically illustrating a layer configuration of No. 0, where 201 is a conductive support, and 202 is a light receiving layer made of a-Si. Such an electrophotographic light receiving member is generally
The conductive support 201 is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, and a plasma CV are formed on the support.
A photosensitive layer 202 made of a-Si is formed by a film forming method such as a method D. Among them, a plasma CVD method, that is, a method in which a raw material gas is decomposed by direct current, high frequency, or microwave glow discharge to form an a-Si deposited film on a support has been put to practical use.

Japanese Patent Application Laid-Open No. 56-83746 discloses an electrophotographic apparatus comprising a conductive support and an a-Si (hereinafter referred to as "a-Si: X") photoconductive layer containing a halogen atom as a constituent element. Light receiving members have been proposed. In this publication, a-Si contains 1 to 40 atomic% of halogen atoms to compensate for dangling bonds, reduce the density of localized states in the energy gap, and reduce the light emission of the electrophotographic light-receiving member. It is said that electrical and optical characteristics suitable as a conductive layer can be obtained.

Japanese Patent Application Laid-Open No. 58-108544 discloses a conductive support, a hydrogen atom or a halogen atom, and a first layer region showing a-Si: H, X photoconductive layer component. There has been proposed a photoconductive member having an amorphous layer including a second layer region made of an amorphous material containing silicon atoms, carbon atoms, halogen atoms, and hydrogen atoms as constituent elements.

In Japanese Patent Application Laid-Open No. 58-219560, amorphous hydrogenated and / or fluorinated silicon carbide (hereinafter referred to as "a-SiC: H, F") contains an element of Group IIIA of the periodic table. An electrophotographic photoreceptor having a surface layer has been proposed.

Japanese Patent Application Laid-Open Nos. 60-67950 and 60-67951 propose a photoreceptor having a translucent insulating overcoat layer containing carbon, fluorine and oxygen in a-Si. I have.

[0009]

However, the conventional electrophotographic light-receiving member having a photoconductive layer made of an a-Si material has a low electrical resistance, such as dark resistance, photosensitivity and photoresponsiveness. In terms of mechanical properties, photoconductive properties, and usage environment properties, as well as stability over time and durability, individual properties have been improved, but further improvements have been made to improve overall properties. The fact is that there is room to be done.

In particular, at present, higher image quality, higher speed, and higher durability are desired for electrophotographic apparatuses. As a result, in the electrophotographic light receiving member, while further improving the electrical characteristics and photoconductive characteristics, while maintaining high charging ability, high sensitivity,
It is required to greatly increase the durability under any environment.

For example, when an a-Si material is applied to a light-receiving member for electrophotography, if the sensitivity and the dark resistance are to be improved at the same time, there is a case where a residual potential remains in the conventional use. It has been frequently observed that when this type of light receiving member is used for a long period of time, there are many inconveniences such as accumulation of fatigue due to repeated use and occurrence of an afterimage, a so-called "ghost" phenomenon. Conventionally, it has been difficult to achieve both high charging ability and prevention of image deletion at a high level.

In recent years, optical exposure systems, developing devices, transfer devices and the like in electrophotographic apparatuses have been improved in order to improve image characteristics of electrophotographic apparatuses. Improvement in image characteristics has been demanded. In particular, as a result of the improvement in the resolution of the image, the reduction of black or white spot-like image defects, which is generally referred to as "potch", and particularly, the reduction of minute-size "potch" which has not been considered so much in the past. It has become required.
In particular, with regard to “pockets”, most of the causes are abnormal growth of a film called spherical projections, and it is very important to reduce the number of occurrences and prevent the spherical projections from appearing as image defects. Further, when image formation is continuously performed, a phenomenon that “pots” increase from the initial image may be observed, and it is required to reduce such an increase in “pots” during the durability. One of the causes is that the paper dust of the transfer paper accumulates on the separation charger due to the continuous image formation, causing abnormal discharge, and the dielectric breakdown of a part of the electrophotographic light receiving member. A so-called “leak spot” that occurs is included. "Leak spots" are likely to occur selectively in spherical projections, which are abnormal growth of the film, so at the same time as reducing spherical projections,
Improving the electrical withstand voltage of the light receiving member and making it difficult to cause dielectric breakdown is very effective for preventing "leak spots".

In recent years, the use of recycled paper in electrophotographic devices has been increasing as part of the promotion of protection of the global environment. However, in the case of recycled paper, the generation of additives and paper dust in the papermaking process is a new problem. More than paper. Therefore, for example, the surface of the electrophotographic photoconductive member is damaged by an additive such as white clay used as a bleaching agent for recycled paper of old newspaper, and rosin used as a sizing agent (surface treatment agent) is used. There is such a problem that the toner adheres to the surface of the light receiving member to cause a fusing image flow of the toner, and further improvement of the quality of the recycled paper and further improvement of the surface of the electroconductive photoconductive member have been demanded.

Therefore, from the viewpoint of reducing image defects and improving durability, the electrophotographic light-receiving member maintains abnormal electrical and photoconductive characteristics while maintaining abnormal growth that causes image defects. It has been required to prevent the occurrence of cracks and improve the electrical withstand voltage so as to greatly extend the durability performance in all environments.

In recent years, in order to reduce the manufacturing cost of the electrophotographic light-receiving member, for example, the electrophotographic light-receiving member is kept at a high deposition rate by a deposition film forming method such as a microwave plasma CVD method described later. Is formed, non-uniformity occurs in the film quality, and a-S
There was a problem that minute cracks and peeling occurred in the i-film, and the adhesion between the layers was reduced, thereby reducing the yield in productivity. Therefore, while the properties of the a-Si material itself are improved, the layer configuration of the electrophotographic light receiving member is designed so that all of the above-mentioned problems are solved when designing the electrophotographic light receiving member. It is required that the chemical composition of each layer, the preparation method, and the like be improved from a comprehensive viewpoint.

The present invention has been made in view of the above points, and has various problems in a light receiving member for electrophotography having a conventional light receiving layer made of a material containing silicon atoms as a base as described above. It is intended to solve the problem.

That is, the main objects of the present invention are electrical,
Optical and photoelectric properties are virtually always stable without depending on the usage environment, excellent in light fatigue resistance, do not cause deterioration phenomenon even after repeated use, especially excellent in image properties and durability, An object of the present invention is to provide an electrophotographic light-receiving member having a light-receiving layer composed of a material containing silicon atoms as a base material and having no or almost no residual potential.

Another object of the present invention is to provide a photoreceptor for electrophotography, which has a sufficient charge retention ability during a charging process for forming an electrostatic image, so that ordinary electrophotography is extremely difficult. An object of the present invention is to provide an electrophotographic light-receiving member having a light-receiving layer composed of a material containing silicon atoms as a base material and exhibiting excellent electrophotographic characteristics that can be effectively applied.

Another object of the present invention is to easily obtain a high-quality image having a high density, a clear halftone and a high resolution without any increase in image defects or image deletion during long-term use. An object of the present invention is to provide an electrophotographic light receiving member having a light receiving layer composed of a material having silicon atoms as a base.

Still another object of the present invention is to provide an electrophotographic light having a light receiving layer composed of a silicon atom-based material having high sensitivity, high S / N ratio characteristics and high electric breakdown voltage. It is to provide a receiving member.

[0021]

Means for Solving the Problems] light-receiving member of the present invention,
In a light receiving member in which a photoconductive layer composed of a non-single-crystal material having silicon atoms as a base material and a surface layer are sequentially laminated on a conductive support, the photoconductive layer is composed of silicon atoms.
When formed by a hydrogen atom or a halogen atom, said surface layer is a silicon atom, a carbon atom, a hydrogen atom or a halogen atom, a periodic table Group III element, with further contains oxygen atoms or nitrogen atoms, the outermost surface Or the most
The carbon atom content near the surface is
70 atom% or more and 90 atom% or less based on the sum of carbon atoms
Characterized in that it is a.

Another feature of the light- receiving member of the present invention is that the light- receiving member has a light-receiving layer composed of a photoconductive layer and a surface layer on a conductive support. An atom as a base, a non-single-crystal material containing a hydrogen atom or a halogen atom, the surface layer is made of a non-single-crystal material having a silicon atom as a base material, and the surface layer is a hydrogen atom, a halogen atom, An oxygen atom and a nitrogen atom are simultaneously contained, and the content of the oxygen atom and / or the nitrogen atom is 1 × 10 ⁻⁴ to 30 at% or less, and the sum of the content of the hydrogen atom and the halogen atom is 1 × 10 ^-5
~ Is 80 or less atomic%, and the content of the periodic table Group III element state, and are less 1 × 10 ⁵ atomic ppm, and the light
The conductive layer further comprises a Group III or V element of the periodic table.
It is to contain .

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

In particular, the increase in "leak spots" during the continuous image formation is extremely small, the abrasion resistance and the moisture resistance are excellent, the electric characteristics thereof are stable, and the high sensitivity and the high SN ratio are obtained. It has a high density, a clear halftone, and a high-resolution, high-quality image can be stably obtained repeatedly because it has excellent repeated use characteristics and electrical withstand voltage. . Further, the present invention can be applied to the formation of an image based on a digital signal.

That is, in the present invention, the hydrogen atoms and / or halogen atoms contained in the photoconductive layer compensate for the dangling bonds of silicon atoms, thereby improving the layer quality, especially the photoconductive characteristics. Demonstrate.

Further, the surface layer is mainly composed of silicon atoms, and carbon atoms, hydrogen atoms, halogen atoms, and periodic table II.
By simultaneously containing a Group I element and an oxygen atom or a nitrogen atom, the electric breakdown voltage can be significantly improved by a synergistic effect of these elements. As a result, even if spherical protrusions, which are abnormal growth of the film, are present to some extent, they can be very rarely caused as image defects such as “pocks”. In addition, at the time of endurance, even if an abnormal discharge occurs in the separation charger in the electrophotographic process, a part of the light receiving member is not broken down and the occurrence of "leak spots" can be extremely reduced.

Further, even when recycled paper is used during durability, the surface layer mainly composed of silicon atoms has carbon atoms, hydrogen atoms, halogen atoms, Group III elements of the periodic table, and oxygen atoms or By simultaneously containing nitrogen atoms, the surface hardness is improved by the synergistic effect, and the occurrence of surface scratches due to additives in the recycled paper can be prevented. Further, it is possible to effectively prevent the sizing agent such as rosin, which is often contained in the recycled paper, from adhering to the surface of the light receiving member, and it is possible to extremely reduce the fusion of the toner and the image deletion during long-term use.

Further, the same effect can be obtained when the oxygen atom and the nitrogen atom are contained in both atoms contained in the surface layer, and the effect is not changed when both are contained simultaneously.

Hereinafter, the light receiving member for electrophotography of the present invention will be described in detail with reference to the drawings.

FIGS. 1 and 2 are schematic diagrams schematically illustrating a preferred layer structure of the electrophotographic light-receiving member of the present invention.

An electrophotographic light receiving member 1100 shown in FIG.
Is a conductive support 11 for an electrophotographic light-receiving member.
01, a photoconductive layer 1102 composed of non-Si: H, X, a non-Si: H composed of at least a carbon atom, a halogen atom, a Group III element of the periodic table,
Surface layer 110 further containing oxygen or nitrogen atoms
A light receiving layer 1104 having a layer configuration consisting of
The light receiving layer 1104 has a free surface 1105.

The electrophotographic light receiving member 12 shown in FIG.
00 denotes a charge injection blocking layer 1204 between the photoconductive layer 1202 made of Si: H, X and the conductive support 1201.
It is essentially the same as the electrophotographic light receiving member 1100 shown in FIG. The light receiving layer 2105 has a free surface 2106. Support The conductive support used in the present invention includes, for example, Al, Cr, Mo, Au, In, Nb, Te, V,
Examples include metals such as Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. Further, a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, and polyamide, an electrically insulating support such as glass and ceramic, at least on a side on which a light receiving layer is formed. A support whose surface is conductively treated can also be used.

Further, it is more preferable that the surface on the side opposite to the side on which the light receiving layer is formed is subjected to a conductive treatment.

The shape of the support may be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface.
The thickness is appropriately determined so that a desired electrophotographic light-receiving member can be formed. However, when flexibility as the electrophotographic light-receiving member is required, the function as a support is required. It can be made as thin as possible within a range that can be fully demonstrated. However, due to the manufacture and handling of the support,
The thickness is usually 10 μm or more from the viewpoint of mechanical strength and the like.

In particular, when image recording is performed using coherent light such as laser light, it appears in a visible image.
To eliminate image defects due to so-called interference fringe patterns,
Irregularities may be provided on the surface of the support.

The irregularities provided on the surface of the support are described in
It is formed by a known method described in JP-A-168156, JP-A-60-178457, JP-A-60-225854 and the like.

As another method for eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, a concave-convex shape formed by a plurality of spherical trace depressions may be provided on the surface of the support. That is, the surface of the support has irregularities smaller than the resolution required for the electrophotographic light-receiving member,
Moreover, the unevenness is due to a plurality of spherical trace depressions. The irregularities due to the plurality of spherical trace dents provided on the surface of the support can be created by a known method described in JP-A-61-231561. Photoconductive layer The photoconductive layer in the present invention has a silicon atom as a base,
It is composed of non-Si: H, X containing at least a hydrogen atom and / or a halogen atom, and has desired photoconductive properties.

Hydrogen atoms and / or halogen atoms contained in the photoconductive layer compensate for dangling bonds of silicon atoms, and are effective in improving the quality of the layer, especially in the photoconductive characteristics. The content of the hydrogen atom or the halogen atom, or the sum of the content of the hydrogen atom and the content of the halogen atom is preferably 1 to
The content is 40 at%, more preferably 5 to 35 at%, and most preferably 10 to 30 at%.

Halogen atom (X) contained in photoconductive layer
Are preferably fluorine, chlorine, bromine and iodine, and fluorine and chlorine are particularly desirable.

In the present invention, the photoconductive layer is formed by a method of forming a vacuum deposited film by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. Specifically, for example, a glow discharge method (low-frequency CVD method, high-frequency C
AC discharge CVD such as VD method or microwave CVD method
Method, DC discharge CVD method, etc.), sputtering method, vacuum deposition method, ion plating method, optical CVD
And a thin film deposition method such as a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the electrophotographic light-receiving member to be produced. The glow discharge method, the sputtering method, and the ion plating method are preferable because the conditions for manufacturing the electrophotographic light-receiving member having characteristics are relatively easily controlled. These methods may be used together in the same apparatus system. For example, to form a non-Si: H, X photoconductive layer by a glow discharge method, a source gas for supplying Si capable of supplying silicon atoms (Si) and a hydrogen atom (H) are basically used. A source gas for supplying H that can be supplied and a source gas for supplying X that can supply a halogen atom (X) are introduced in a desired gas state into a reaction vessel in which the inside can be decompressed. Glow discharge is caused to occur, and a layer made of non-Si: H, X may be formed on the surface of a predetermined support previously set at a predetermined position.

The substances which can be used as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , and Si ₃ H
₈ , silicon hydrides (silanes) in a gaseous state such as Si ₄ H ₁₀ or the like, which can be gasified, can be used effectively. In this respect, SiH ₄ and Si ₂ H ₆ are preferred. Further, these Si supply source gases may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

Effective as the halogen atom supply gas used in the present invention are many halogen compounds, such as halogen gas, halogen compounds, interhalogen compounds, and gaseous or halogen-substituted silane derivatives. Preference is given to halogenated compounds which can be gasified. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound.

The halogen compounds that can be suitably used in the present invention include, specifically, fluorine gas (F ₂ ), chlorine gas (Cl ₂ ), bromine gas (Br ₂ ), iodine gas (I ₂ ), BrF, ClF, ClF ₃ , BrF ₃ , Br
Interhalogen compounds such as F ₅ , IF ₃ and IF ₇ can be mentioned. Specific examples of the silicon compound containing a halogen atom, ie, a silane derivative substituted with a halogen atom, include, for example, SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiB
Silicon halides such as r ₄ are preferred.

When the characteristic light receiving member for electrophotography of the present invention is formed by glow discharge or the like by employing such a silicon compound containing a halogen atom, silicon hydride gas as a gas for supplying Si is used. Even without using, a photoconductive layer composed of non-Si: H, X containing a halogen atom can be formed on a predetermined support, but hydrogen atoms introduced into the formed photoconductive layer can be removed. In order to further facilitate the control of the introduction ratio, it is preferable to form a layer by mixing a desired amount of a hydrogen gas or a silicon compound gas containing a hydrogen atom with these gases. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

In the present invention, the above-mentioned halides or silicon compounds containing halogens are effectively used as the halogen atom supply gas. In addition, hydrogen halides such as HF, HCl, HBr and HI are used. ,
SiH ₃ F, SiH ₂ F ₂ , SiHF ₃ , SiH ₂ I ₂ , Si
Gaseous or gasifiable substances such as halogen-substituted silicon hydrides such as H ₂ Cl ₂ , SiHBr ₂ and SiHBr ₃ can also be cited as effective starting materials for forming the photoconductive layer. Among these substances, the halide containing a hydrogen atom introduces a halogen atom into the layer at the time of forming the photoconductive layer, and at the same time, introduces a hydrogen atom which is extremely effective in controlling electric or photoelectric characteristics. Therefore, in the present invention, it is used as a suitable halogen atom supply gas.

In order to structurally introduce hydrogen atoms into the photoconductive layer, in addition to the above, H ₂ , or SiH ₄ , Si ₂ H ₆ , S
The discharge can also be performed by causing silicon hydride such as i ₃ H ₈ and Si ₄ H ₁₀ and silicon or a silicon compound for supplying Si to coexist in a reaction vessel to generate a discharge.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer, for example, the temperature of the support, the raw material used for containing hydrogen atoms or halogen atoms, are introduced into a reaction vessel. The amount to be introduced, the discharge power, and the like may be controlled.

Further, in the present invention, it is preferable that the photoconductive layer contains an atom (M) for controlling conductivity as necessary. The atoms controlling the conductivity may be contained in the photoconductive layer in a state of being uniformly distributed,
Alternatively, there may be portions contained in a non-uniform distribution state in the layer thickness direction.

The above-mentioned atoms for controlling conductivity include so-called impurities in the field of semiconductors, and include atoms belonging to Group III of the periodic table that provide p-type conduction characteristics (hereinafter referred to as “Group III atoms”). Or an atom belonging to Group V of the periodic table that provides n-type conduction characteristics (hereinafter referred to as “Group V atom”).

As the Group III atom, specifically, B
(Boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), and the like, and B, Al, and Ga are particularly preferable. Specific examples of Group V atoms include P (phosphorus), As (arsenic), Sb (antimony), and Bi (bismuth). In particular, P and As
Is preferred.

The content of the atom (M) for controlling the conductivity contained in the photoconductive layer is preferably from 1 × 10 ^{−3 to} 5 × 10 ^−3.
× 10 ⁴ atomic ppm, more preferably 1 × 10 ^-2 to 1 ×
The concentration is 10 ⁴ atomic ppm, optimally 1 × 10 ^{−1 to} 5 × 10 ³ atomic ppm.

In order to structurally introduce a conductivity controlling atom, for example, a group III atom or a group V atom into the photoconductive layer, a raw material for introducing a group III atom must be used in forming the layer. Alternatively, a raw material for introducing a group V atom may be introduced in a gaseous state into a reaction vessel together with another gas for forming a photoconductive layer. As a source material for introducing a group III atom or a source material for introducing a group V atom, a material which is gaseous at normal temperature and normal pressure or which can be easily gasified at least under layer forming conditions is employed. It is desirable. As a raw material for introducing a group III atom, specifically, for introducing a boron atom, B ₂ H ₆ , B
_{4 H 10, B 5 H 9} , B 5 H 11, B 6 H 10, B 6 H 12, B 6 H 14
And borohydrides such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaC
l ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl _{3, and the} like.

In the present invention, the starting material for introducing a group V atom is effectively used for introducing a phosphorus atom, such as phosphorus hydride such as PH ₃ and P ₂ H ₄ , PH ₄ I and PF _3. , P
Phosphorus halides such as F ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , PI _{3 and the} like can be mentioned. In addition, AsH ₃ , As
F ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , Sb
F ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , Bi
Cl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a group V atom.

The raw materials for introducing atoms for controlling the conductivity may be H ₂ , He, Ar, Ne if necessary.
May be used after being diluted with such a gas.

Further, the photoconductive layer of the light receiving member of the present invention contains at least one element selected from Group Ia, IIa, VIa, and VIII of the periodic table in an amount of about 0.1 to 10000 atomic ppm. May be. The element may be uniformly distributed in the photoconductive layer, or may be uniformly distributed in the photoconductive layer, but may be non-uniformly distributed in the film thickness direction. There may be a part to contain.

As the Group Ia atom, specifically, Li
(Lithium), Na (sodium), and K (potassium). Group IIa atoms include Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), and Ba (barium). And the like.

Specific examples of Group VIa atoms include Cr (chromium), Mo (molybdenum) and W (tungsten). Group VIII atoms include Fe (iron), Co (cobalt), Ni (nickel)
And the like.

In the present invention, the thickness of the photoconductive layer is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 5 to 50.
μm, more preferably 10 to 40 μm, and most preferably 15 to
The thickness is desirably 30 μm, and such a film thickness is advantageous for generating photocarriers extremely corresponding to the intensity of irradiated light.

N having characteristics capable of achieving the object of the present invention.
To form a photoconductive layer of on-Si: H, F,
It is necessary to appropriately set the temperature of the support and the gas pressure in the reaction vessel as desired.

The temperature (Ts) of the support is appropriately selected in an optimum range according to the layer design, but is usually preferably 20 to 500 ° C., more preferably 50 to 480 ° C.
Optimally, it is 100 to 400 ° C.

The gas pressure in the reaction vessel is also appropriately selected in an optimum range in accordance with the layer design, but is usually 1 × 10 ^{-5 to} 100 Torr, preferably 5 × 1 Torr.
0 ^{-5 to} 30 Torr, optimally 1 × 10 ^{-4 to} 10 Torr
r is preferable.

In the present invention, the preferable ranges of the temperature of the support and the gas pressure for forming each of the above-mentioned layers include the above-mentioned ranges, and these layer-forming factors are usually determined independently and separately. Instead, it is desirable to determine the optimum value of each layer forming factor based on mutual and organic relations to form a photoconductive layer having desired properties.

Further, in the present invention, it is desirable that a layer region containing at least aluminum atoms, silicon atoms, and hydrogen atoms in a non-uniform distribution state in the layer thickness direction is provided on the support side of the photoconductive layer. Surface layer The surface layer in the present invention is composed of a non-single-crystal material having a silicon atom as a base, and at least a carbon atom, a hydrogen atom, a halogen atom, a Group III element of the periodic table, and an oxygen atom or a nitrogen atom at the same time. contains.

The silicon atoms, hydrogen atoms, carbon atoms, halogen atoms, Group III elements of the periodic table, and oxygen atoms or nitrogen atoms contained in this layer may be evenly distributed in this layer. Although it may be contained in the surface layer evenly, it may be distributed unevenly in the layer thickness direction.

The silicon atom, hydrogen atom, carbon atom, halogen atom and Group III element of the periodic table, and furthermore the oxygen atom and the nitrogen atom contained in this layer, have a synergistic effect due to their simultaneous inclusion. The effect improves electrical pressure resistance, and is effective in reducing "pocks" and "leak spots".

In the case of using recycled paper at the time of endurance, even if the surface layer mainly composed of silicon atoms is used,
By simultaneously containing a carbon atom, a hydrogen atom, a halogen atom, a Group III element of the periodic table, and an oxygen atom or a nitrogen atom, surface hardness is improved, and a sizing agent such as rosin of recycled paper is used as a light receiving member. It is effective in preventing the toner from adhering to the surface and eliminating toner fusion and image deletion during long-term use.

The content of carbon atoms is preferably 70 to 90 at%, more preferably 70 to 86 at%, and most preferably 70 to 83 at% based on the sum of silicon atoms and carbon atoms. Is desirable.

The sum of the contents of hydrogen and halogen atoms is
Preferably 1 × 10 ^-5 to 80 atomic%, more preferably 5 ×
10 ^-5 to 75 atomic%, optimally 1 × 10 ^-4 to 70 atomic%
It is desirable that

Specific examples of Group III elements of the periodic table include B (boron), Al (aluminum), Ga (gallium), In (indium), and Tl (thallium). preferable. The content of the Group III element of the periodic table is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁵ atomic ppm, more preferably 5 × 10 ^{−5 to} 5 × 10 ⁵ atomic ppm, and most preferably 1 × 10 ⁻⁵ to 5 × 10 ⁵ atomic ppm. It is desirable that the concentration be 10 ^{−4 to} 3 × 10 ⁴ atomic ppm.

The content of oxygen atoms is preferably 1 × 10 ^-4 to
It is desirable that the content be 30 atomic%, optimally 3 × 10 ^{-4 to} 20 atomic%.

The content of the nitrogen atom is preferably 1 × 10 ^-4 to
It is desirable that the content be 30 atomic%, optimally 3 × 10 ^{-4 to} 20 atomic%.

When oxygen and nitrogen atoms are simultaneously contained, the sum of these contents is preferably 1 × 10 ^-4 to
It is desirable that the content be 30 atomic%, optimally 3 × 10 ^{-4 to} 20 atomic%.

In the present invention, as a material which can be a raw material for introducing carbon atoms, a material which is gaseous at ordinary temperature and normal pressure or which can be easily gasified at least under layer forming conditions is desirable.

Starting materials that can be effectively used as a source gas for introducing carbon atoms (C) are, for example, saturated hydrocarbons having 1 to 5 carbon atoms, having C and H as constituent atoms. 2-4 ethylene hydrocarbons, 2-3 carbon atoms
Acetylene-based hydrocarbons.

Specifically, as the saturated hydrocarbon, methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C
₃ H _8), n- butane _{(n-C 4 H 10)} , pentane (C ₅ H
₁₂ ), Ethylene hydrocarbons include ethylene (C
₂ H ₄ ), propylene (C ₃ H ₆ ), butene-1 (C
₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C
₄ H ₈ ), pentene (C ₅ H ₁₀ ), and acetylene-based hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and the like.

Examples of the raw material gas containing Si and C as constituent atoms include alkyl silicides such as Si (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ .

[0077] In addition, in addition to the introduction of the carbon atoms (C), from the viewpoint allows the introduction of fluorine atoms, CF _{4,
CF 3, C 2 F 6,} C 3 F 8, can be mentioned C ₄ F fluorocarbon compounds such as _8.

In the present invention, examples of the starting material which can be effectively used as a gas for introducing oxygen atoms (O) include oxygen (O ₂ ) and ozone (O ₃ ).

In the present invention, the starting material which is effectively used as a gas capable of introducing a nitrogen atom (N) is gaseous at ordinary temperature and normal pressure or easily gasified at least under the above-mentioned surface layer forming conditions. What you get is desirable. For example, nitrogen (N ₂ ), ammonia and the like can be mentioned.

As substances for simultaneously introducing oxygen atoms and nitrogen atoms, nitrogen monoxide (NO) and nitrogen dioxide (N
O ₂ ), nitrogen monoxide (N ₂ O), nitrogen trioxide (N
₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen pentoxide (N ₂
O ₅ ).

In addition to the introduction of carbon atoms (C), in addition to the introduction of oxygen atoms, CO, C
Compounds such as O ₂ can be mentioned.

Further, in the surface layer of the light receiving member of the present invention,
At least one element selected from Group Ia, Group IIa, Group VIa and Group VIII of the periodic table is 0.1 to 10000 atoms p
pm. The element may be uniformly distributed in the photoconductive layer, or may be uniformly distributed in the photoconductive layer, but may be non-uniformly distributed in the film thickness direction. There may be a part to contain.

As the Group Ia element, specifically, Li
(Lithium), Na (sodium), and K (potassium). Examples of Group IIa elements include Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), and Ba (barium). And the like.

As the group VIa element, specifically, C
r (chromium), Mo (molybdenum), W (dangsten), and the like.
e (iron), Co (cobalt), Ni (nickel) and the like.

In the present invention, the thickness of the surface layer is preferably from 0.01 to 30 μm, more preferably from 0.05 to 20 μm, from the viewpoints of obtaining desired electrophotographic characteristics and economic effects. Is set to 0.1 to 10 μm.

In the present invention, in order to form a surface layer composed of non-SiC: H and containing a hydrogen atom, a halogen atom, a Group III element of the periodic table, and further an oxygen atom and a nitrogen atom, the aforementioned photoconductive layer is used. A vacuum deposition method similar to the method of forming the layer is employed.

In forming a surface layer having characteristics capable of achieving the object of the present invention, the temperature and gas pressure of the support are important factors that influence the characteristics of the surface layer. The temperature of the support is appropriately selected in an optimum range, but is preferably 20 to 50.
0 ° C, more preferably 50-480 ° C, optimally 100
To 450 ° C.

The optimum gas pressure in the reaction vessel is also appropriately selected, but is preferably 1 × 10 ^{-5 to} 100 Torr, more preferably 5 × 10 ^{-5 to} 30 Torr, and most preferably 1 × 10 ^{-5 to} 30 Torr.
10 ^{−4 to} 10 Torr.

In the present invention, the preferable ranges of the temperature of the support and the gas pressure for forming the surface layer include the above-mentioned ranges, and these layer forming factors are usually determined independently and separately. Instead, in order to form a surface layer having desired properties, it is desirable to determine the optimum value of each layer forming factor based on mutual and organic relations. Charge Injection Blocking Layer In the electrophotographic light-receiving member of the present invention, a charge injection blocking layer having a function of blocking charge injection from the conductive support side is provided between the photoconductive layer and the conductive support. Is also good.
That is, the charge injection blocking layer has a function of preventing charge from being injected from the support side to the photoconductive layer side when the photoreceptive layer receives a charge treatment of a certain polarity on its free surface. Such a function is not exhibited when it is subjected to a charging treatment having a polarity of, that is, it has a so-called polarity dependency. In order to provide such a function, the charge injection blocking layer contains a relatively large amount of a substance that controls conductivity that provides one conductivity type.

The conductivity controlling substances contained in this layer may be distributed evenly and uniformly in this layer, or may be contained evenly in the thickness direction of the layer. There may be a portion containing a state that is uniformly distributed.
When the distribution concentration is non-uniform, it is preferable that the compound be contained so as to be distributed more on the support side.

As the substance for controlling conductivity contained in the charge injection blocking layer, there can be mentioned a so-called impurity in the field of semiconductors, and an atom belonging to Group III of the periodic table which gives p-type conduction characteristics (hereinafter referred to as “ (Group III atoms) or an atom belonging to Group V of the periodic table that provides n-type conduction characteristics (hereinafter referred to as “Group V atoms”) can be used.

As the Group III atom, specifically, B
(Boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), and the like, and B, Al, and Ga are particularly preferable. Specific examples of Group V atoms include P (phosphorus), As (arsenic), Sb (antimony), and Bi (bismuth). In particular, P and As
Is preferred.

In the present invention, the content of the substance (M) for controlling conductivity contained in the charge injection blocking layer is as follows:
It is appropriately determined as desired so that the object of the present invention can be effectively achieved, but is preferably 1 to 5 × 10 ⁵ atomic ppm, more preferably ^{5 to} 1 × 10 ⁵ atomic ppm, and most preferably 10 to 10 × 10 ⁵ atomic ppm. 5 × 10 ⁴ atomic ppm.

Further, by including at least one of carbon atoms, nitrogen atoms and oxygen atoms in the charge injection blocking layer, the adhesion between the charge injection blocking layer and another layer provided in direct contact with the charge injection blocking layer is improved. Further improvement can be achieved.

The carbon atoms, nitrogen atoms or oxygen atoms contained in this layer may be distributed evenly and uniformly in this layer, or may be contained evenly in the thickness direction of the layer. May be present in a non-uniformly distributed state.

However, in any case, it is important from the viewpoint of making the characteristics uniform in the in-plane direction that the content is uniformly distributed in the in-plane direction parallel to the surface of the support. is there.

In the present invention, carbon atoms and / or nitrogen atoms and / or
Alternatively, the content of the oxygen atom is appropriately determined so that the object of the present invention is effectively achieved. However, in the case of one kind, the amount is two times or more. 10 ^{-3 to} 90 atomic%, more preferably 5 × 10 ^-3 to
80 atomic%, optimally 1 × 10 ^-2 to 50 atomic%.

Further, the hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer in the present invention have an effect of improving the film quality by compensating for dangling bonds existing in the layer. The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the charge injection blocking layer is preferably 1 to 70 atomic%, more preferably 5 to 60 atomic%, and most preferably 17 to 50 atomic%. It is desirable.

Further, the charge injection blocking layer of the photoreceptor according to the present invention contains at least one element selected from Group Ia, IIa, VIa and VIII of the periodic table in the range of 0.1 to 10,000.
You may contain about atomic ppm. These elements may be evenly distributed in the charge injection blocking layer, or may be uniformly contained in the charge injection blocking layer, but may be unevenly distributed in the film thickness direction. There may be a part to be contained in a state where it is used. Specific examples of the Group Ia atom include Li (lithium), Na (sodium), and K (potassium).
e (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium)
And the like.

Specific examples of group VIa atoms include Cr (chromium), Mo (molybdenum), and W (tungsten). Group VIII atoms include Fe (iron), Co (cobalt), Ni (nickel)
And the like.

In the present invention, the thickness of the charge injection blocking layer is preferably from 0.01 to 200 μm, more preferably from 0.05 to 15 μm, from the viewpoint of obtaining desired electrophotographic characteristics and economic effects. , Optimally 0.1-10μ
m.

In the present invention, as a method for forming the charge injection blocking layer, the same vacuum deposition method as the above-described method for forming the photoconductive layer is employed.

When forming a charge injection blocking layer having characteristics capable of achieving the object of the present invention, the temperature and gas pressure of the support are important factors that influence the characteristics of the surface layer. The temperature of the support is appropriately selected in an optimum range.
The temperature is from 0 to 500C, more preferably from 50 to 480C, and most preferably from 100 to 450C.

The gas pressure in the reaction vessel is appropriately selected in an optimum range, but is preferably 1 × 10 ^{−5 to} 100 Torr, more preferably 5 × 10 ^{−5 to} 30 Torr, and most preferably 1 × 10 ^{−5 to} 30 Torr.
10 ^{-4 to} 10 Torr.

In the present invention, the preferable ranges of the temperature and the gas pressure of the support for forming the charge injection blocking layer include the above-mentioned ranges. However, these layer forming factors are usually determined independently and separately. Is not something
In order to form a surface layer having desired properties, it is desirable to determine the optimum value of each layer forming factor based on mutual and organic relationships.

In the present invention, when the charge injection blocking layer is provided between the photoconductive layer and the conductive support, at least aluminum atoms, silicon atoms, and hydrogen atoms are provided on the support side of the charge injection blocking layer. It is desirable to have a layer region which contains in a layer thickness direction in a non-uniform distribution state.

Hereinafter, an apparatus and a method for forming a deposited film by high frequency plasma CVD and microwave plasma CVD will be described in detail.

FIG. 4 shows a high-frequency plasma CVD (hereinafter referred to as “R”).
FIG. 7 is a schematic configuration diagram showing an example of an apparatus for manufacturing a photoreceptor member for electrophotography by a method described as “F-PCVD”).
FIG. 5 and FIG. 5 are schematic structural diagrams showing an example of a deposited film forming apparatus for forming a deposited film for a light receiving member for electrophotography by a microwave plasma CVD (hereinafter referred to as “μW-PCVD”) method. FIG. 6 is an explanatory view of an apparatus for manufacturing an electrophotographic light-receiving member by the μW-PCVD method. The shape of the reaction furnace of this deposition film forming apparatus may be circular, square, or polygonal.

The configuration of the apparatus for manufacturing a deposited film by the RF-PCVD method shown in FIG. 4 is as follows. This apparatus is roughly divided into a deposition apparatus 3100 and a raw material gas supply apparatus 320.
0, an exhaust device (not shown) for reducing the pressure inside the reaction vessel 3111. A cylindrical support 3112, a heater 3113 for heating the support, a source gas introduction pipe 3114 are installed in a reaction vessel 3111 in the deposition apparatus 3100, and a high-frequency matching box 3115 is connected.

The raw material gas supply device 3200 includes SiH ₄ ,
Cylinders 3221 to 226 and valves 3231 to 323 for source gases such as SiF ₄ , H ₂ , CH ₄ , B ₂ H ₆ and PH _3.
6, 3241 to 246, 3251 to 256, and mass flow controllers 3211 to 216, and a cylinder for each source gas is connected to a gas introduction pipe 3114 in the reaction vessel 3111 via a valve 3260.

The formation of a deposited film using this apparatus can be performed, for example, as follows.

First, the cylindrical support 3112 is set in the reaction vessel 3111, and the inside of the reaction vessel 3111 is evacuated by a not-shown exhaust device (for example, a vacuum pump). continue,
The cylindrical support 31 is heated by the support heating heater 3113.
The temperature of No. 12 is controlled to a predetermined temperature of 20 ° C to 500 ° C.

The source gas for forming the deposited film is supplied to the reaction vessel 311.
In order to make the gas flow into the valve 1, the valves 3231 to 331 of the gas cylinder are used.
236, confirming that the leak valve 3117 of the reaction vessel is closed, and checking the inflow valves 3241 to 324
6. Outflow valves 3251 to 256, auxiliary valve 326
Make sure that the main valve 3 is open.
Open 118 to open reaction vessel 3111 and gas pipe 31
Exhaust 16.

Next, the vacuum gauge 3119 reads about 5 × 10 ^−6.
When reaching Torr, the auxiliary valve 3260 and the outflow valves 3251 to 256 are closed.

Thereafter, each gas is introduced from the gas cylinders 3221 to 226 by opening the valves 3231 to 236.
2 kg of each gas pressure by pressure regulators 3261 to 3266
/ Cm ² . Next, the inflow valves 3241-32
46 is gradually opened to introduce each gas into the mass flow controllers 3211 to 3216.

After the preparation for film formation is completed as described above, the photoconductive layer and the surface layer are formed on the cylindrical support 3112.

When the temperature of the cylindrical support 3112 reaches a predetermined temperature, necessary ones of the outflow valves 3251 to 256 and the auxiliary valve 3260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 3221 to 226 to the gas introduction pipe 3.
It is introduced into the reaction vessel 3111 via 114. Next, the mass flow controllers 3211 to 216 adjust each source gas to a predetermined flow rate. that time,
The opening of the main valve 3118 is adjusted while watching the vacuum gauge 3119 so that the pressure in the reaction vessel 3111 becomes a predetermined pressure of 1 Torr or less. When the internal pressure is stable,
An RF power source (not shown) is set to a desired power, and a reaction vessel 3111 is set through a high-frequency matching box 3115.
RF power is introduced into the device to generate an RF glow discharge.
The raw material gas introduced into the reaction vessel is decomposed by the discharge energy, and a deposited film mainly containing predetermined silicon is formed on the cylindrical support 3112. After the formation of the desired film thickness, the supply of the RF 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 light receiving layer having a desired multilayer structure is formed.

When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed, and each gas is supplied to the reaction vessel 3111.
, Outflow valves 3251-256 to reaction vessel 311
In order to avoid remaining in the piping leading to 1, the operation of closing the outflow valves 3251 to 256, opening the auxiliary valve 3260, and further fully opening the main valve 3118 to once evacuate the system to a high vacuum is performed as necessary. Do it.

In order to uniform the film formation, the cylindrical support 3112 is rotated at a predetermined speed by a driving device (not shown) during the film formation.

It goes without saying that the above-mentioned gas types and valve operations are changed according to the conditions for forming each layer.

The heating method of the support may be a heating element having a vacuum specification, and more specifically, an electric resistance heating element such as a winding heater of a sheath heater, a plate heater, or a ceramic heater, a halogen lamp, an infrared lamp, or the like. A heat radiating lamp heating element such as a lamp, a heating element using a liquid, a gas, or the like as a heating medium and a heat exchange unit may be used. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum, and copper, ceramics, heat-resistant polymer resins, and the like can be used.

In addition to the above, a method other than providing a reaction vessel other than a reaction vessel, heating, and then transporting the support in a vacuum in the reaction vessel may be used.

Next, a method for manufacturing an electrophotographic light-receiving member formed by microwave plasma CVD will be described.

RF-PC in the manufacturing apparatus shown in FIG.
By replacing the deposition apparatus 3100 by the VD method with the deposition apparatus 4100 shown in FIG. 7 and connecting to the source gas supply apparatus 3200, the μW plasma CV shown in FIGS.
An electrophotographic light-receiving member manufacturing apparatus having the following configuration according to Method D can be obtained.

This apparatus comprises a reaction vessel 4111 having a vacuum-tight structure and capable of reducing pressure, and a raw material gas supply apparatus 320.
0, and an exhaust device (not shown) for reducing the pressure inside the reaction vessel. In the reaction vessel 4111, microwave power is efficiently transmitted into the reaction vessel, and
A microwave power supply (not shown) is provided through a microwave introduction window 4112, a stub tuner (not shown), and an isolator (not shown) formed of a material (for example, quartz glass, alumina ceramics or the like) capable of maintaining vacuum tightness. (Not shown) connected to microwave waveguide 41
13, a cylindrical support 4115 on which a deposited film is to be formed, a heater 4116 for heating the support, a source gas introduction pipe 4117,
An electrode 4118 for applying an external electric bias for controlling the plasma potential is provided.
The inside of 11 is connected to a diffusion pump (not shown) through an exhaust pipe 4121. The raw material gas supply device 3200 is made of SiH
₄ , SiF ₄ , H ₂ , CH ₄ , B ₂ H ₆ and PH _3.
It comprises 236, 3241 to 2246, 3251 to 3256, and mass flow controllers 3211 to 216, and the cylinders for each source gas are connected to a gas introduction pipe 4117 in the reaction vessel via a valve 3260. The space 4 surrounded by the cylindrical support 4115
130 forms a discharge space.

The formation of a deposited film in this apparatus by the μW plasma CVD method can be performed as follows.

First, a cylindrical support 4115 is set in a reaction vessel 4111, and
By rotating 115, the inside of the reaction vessel 4111 is evacuated through an exhaust pipe 4121 by an unillustrated exhaust device (for example, a vacuum pump), and the pressure inside the reaction vessel 4111 is reduced to 1 × 10 ⁻⁷ To.
Adjust to rr or less. Subsequently, the heater 4 for heating the support is used.
By 116, the temperature of the cylindrical support 4115 is heated and maintained at a predetermined temperature of 20 ° C. to 500 ° C.

The source gas for forming the deposited film is supplied to the reaction vessel 411.
In order to make the gas flow into the valve 1, the valves 3231 to 331 of the gas cylinder are used.
236, confirm that the leak valve (not shown) of the reaction vessel is closed, and check the inflow valves 3241 to 32
46, outflow valves 3251 to 256, auxiliary valve 32
After confirming that 60 has been opened, first, the main valve (not shown) is opened to evacuate the reaction vessel 4111 and the gas pipe 4122.

Next, the reading of a vacuum gauge (not shown) was about 5 × 1.
When the pressure reaches 0 ^-6 Torr, the auxiliary valve 3260 and the outflow valves 3251 to 256 are closed.

Thereafter, each gas is introduced from the gas cylinders 3221 to 226 by opening the valves 3231 to 236.
2 kg of each gas pressure by pressure regulators 3261 to 3266
/ Cm ² . Next, the inflow valves 3241-32
46 is gradually opened to introduce each gas into the mass flow controllers 3211 to 3216.

After the preparation for film formation is completed as described above, the photoconductive layer and the surface layer are formed on the cylindrical support 4115.

When the cylindrical support 4115 reaches a predetermined temperature, necessary ones of the outflow valves 3251 to 256 and the auxiliary valve 3260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 3221 to 226 to the gas introduction pipe 4.
117, the discharge space 4130 in the reaction vessel 4111
To be introduced. Next, the mass flow controllers 3211 to 3211
In accordance with 3216, each source gas is adjusted to have a predetermined flow rate. At this time, the pressure in the discharge space 4130 is 1 To
Vacuum gauge (not shown) so as to reach a predetermined pressure of rr or less
And adjust the opening of the main valve (not shown). After the pressure is stabilized, a microwave power supply (not shown) is used to drive a frequency of 500 MHz or more, preferably 2.45G.
, A microwave power source (not shown) is set to a desired power, and μW energy is introduced into the discharge space 4130 through the waveguide 4113 and the microwave introduction window 4112 to generate a μW glow. Causes discharge. At the same time, an electric bias such as a direct current is applied to the electrode 4118 from the power supply 4119. In the discharge space 4130 surrounded by the support 4115 in this way, the introduced source gas is excited by microwave energy and dissociated, and a predetermined deposited film is formed on the cylindrical support 4115. At this time, the layer is rotated at a desired rotation speed by the support rotating motor 4120 in order to make the layer formation uniform.

After the formation of the desired film thickness, the supply of μW 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 light receiving layer having a desired multilayer structure is formed.

When forming each layer, it goes without saying that all outflow valves other than necessary gas are closed, and each gas is supplied to the reaction vessel 4111.
And the reaction vessel 411 from the outflow valves 3251 to 256
In order to avoid remaining in the pipes leading to 1, the operation of closing the outflow valves 3251 to 256, opening the auxiliary valve 3260, and fully opening the main valve (not shown) to once exhaust the system to a high vacuum. Perform as necessary.

It goes without saying that the above-mentioned gas types and valve operations are changed according to the conditions for forming each layer.

The heating method of the support may be a heating element having a vacuum specification, and more specifically, an electric resistance heating element such as a winding heater of a sheath heater, a plate heater, or a ceramic heater, a halogen lamp, an infrared lamp, or the like. Examples of the heating element include a heat radiation lamp heating element such as a lamp, and a heating element using a liquid or a gas as a heating medium and a heat exchange unit. The surface material of the heating means is
Metals such as stainless steel, nickel, aluminum, copper, etc.
Ceramics, heat-resistant polymer resins and the like can be used.

In addition to the above, a method other than providing a reaction vessel other than the reaction vessel, heating, and then transporting the support in the reaction vessel in a vacuum is used.

In the μW-PCVD method, the pressure in the discharge space is preferably not less than 1 mTorr and not more than 100 mTorr.
Torr or less, more preferably 3 mTorr or more and 50 m
Torr or less, most preferably 5 mTorr or more and 30 m
Torr or less. The pressure outside the discharge space only needs to be lower than the pressure inside the discharge space. However, when the pressure inside the discharge space is 100 mTorr or less, it is particularly remarkable.
At mTorr or less, when the pressure inside the discharge space is three times or more the pressure outside the discharge space, the effect of improving the characteristics of the deposited film is particularly large.

As a method for introducing microwaves into the reaction furnace, a method using a waveguide can be mentioned.
Introducing from one or more dielectric windows. At this time, the material of the window for introducing the microwave into the furnace is alumina (Al ₂ O ₃ ), aluminum nitride (Al
N), boron nitride (BN), silicon nitride (SiN), silicon carbide (SiC), silicon oxide (SiO ₂ ), beryllium oxide (BeO), Teflon, polystyrene and other materials with low microwave loss are usually used. Is done.

The electric field generated between the electrode and the support is preferably a DC electric field, and the direction of the electric field is more preferably directed from the electrode to the support. The average magnitude of the DC voltage applied to the electrodes to generate the electric field is 15 V or more and 300 V
Or less, preferably 30 V or more and 200 V or less. The DC voltage waveform is not particularly limited, and various waveforms are effective in the present invention. In other words, any case may be used as long as the direction of the voltage does not change with time. Even a pulsating voltage that changes is effective.

It is also effective to apply an AC voltage. There is no problem with the AC frequency at any frequency.
Practically, 50 Hz or 60 Hz is suitable for a low frequency, and 13.56 MHz is suitable for a high frequency. The AC waveform may be a sine wave, a rectangular wave, or any other waveform,
Practically, a sine wave is suitable. However, at this time, the voltage is
In each case, it refers to the effective value.

The size and shape of the electrode may be any as long as they do not disturb the discharge.
A cylindrical shape of m or more and 5 cm or less is preferable. At this time,
The length of the electrode can be arbitrarily set as long as the electric field is uniformly applied to the support.

The electrode may be made of any material as long as its surface becomes conductive. For example, stainless steel, Al, Cr, Mo, Au, In, Nb, Te, V,
Metals such as Ti, Pt, Pd, and Fe, alloys thereof, and glasses, ceramics, and plastics whose surfaces are subjected to a conductive treatment are usually used.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Example 1 Using a manufacturing apparatus for a photoreceptor member for electrophotography by the RF glow discharge method shown in FIG. The light receiving layer of the light receiving member for electrophotography was formed on the aluminum cylinder of the above.

[0147]

[Table 1] Comparative Example 1 An electrophotographic light-receiving member was produced in the same manner as in Example 1 except that CO ₂ was not used in the surface layer. Comparative Example 2 An electrophotographic light-receiving member was produced in the same manner as in Example 1 except that SiF ₄ was not used in the surface layer. Comparative Example 3 An electrophotographic light-receiving member was produced in the same manner as in Example 1 except that B ₂ H ₆ was not used in the surface layer. Comparative Example 4 An electrophotographic light-receiving member was produced in the same manner as in Example 1 except that CH ₄ and CO ₂ were not used in the surface layer and O ₂ was added to the surface layer.

[0148]

[Table 2] Comparative Example 5 An electrophotographic light-receiving member was produced in the same manner as in Example 1 except that CO ₂ and SiF ₄ were not used in the surface layer. Comparative Example 6 An electrophotographic light-receiving member was produced in the same manner as in Example 1 except that CO ₂ and B ₂ H ₆ were not used in the surface layer. Comparative Example 7 A light receiving member for electrophotography was produced in the same manner as in Example 1 except that SiF ₄ and B ₂ H ₆ were not used in the surface layer. Comparative Example 8 A light receiving member for electrophotography was prepared in the same manner as in Example 1 except that CO ₂ , SiF ₄ and B ₂ H ₆ were not used in the surface layer.

The electrophotographic light-receiving members produced in Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, Comparative Example 5, Comparative Example 6, Comparative Example 7, and Comparative Example 8 were replaced by Canon. The copying machine NP-7550 is installed in an electrophotographic apparatus modified for experiments, and electrophotographic characteristics such as "white spots", "scratch", "image deletion", and "black spots due to toner fusion" in the initial image. After that, a durability test of 2.5 million sheets was performed and "white spots", "scratch", "image deletion",
"Black spots due to toner fusion" were evaluated. Each item was evaluated by the following method. White Pochi Canon All Black Test Chart (Part No. FY9-9
073) was placed on a platen and a white spot having a diameter of 0.2 mm or more within the same area of a copy image obtained when copying was evaluated. Image test A Canon test chart (part number FY9-9058) consisting of characters on a white background is placed on a platen and placed on a 1.5 lu
X-sec light irradiation was performed and a copy was taken. The obtained copy image was observed, and it was evaluated whether fine lines on the image were connected without interruption. However, at this time, when there was unevenness in the image, the evaluation was performed in the entire image area, and the result of the worst part was shown. Black spots due to fusing of toner The Canon white test chart made by Canon was placed on a platen and copied to obtain a copy image having a width of 0.
Black spots of 1 mm × length 0.5 mm or more were evaluated. 340 mm wide of the copy image obtained when the halftone test chart made by Kiz Canon is placed on the platen and copied
(One rotation of the light receiving member for electrophotography) × Scratch having a width of 0.05 mm × length of 0.2 mm or more in an area of 297 mm in height was counted and evaluated.

“White spots”, “scratch”, “image deletion”,
Table 3 shows the results of the initial image before the endurance of “black spots due to toner fusion”, and Table 4 shows the results after the endurance test of 2.5 million sheets.

Regarding “white spots”, “image deletion”, and “black spots due to toner fusion”, ◎ indicates “particularly good” 〇 indicates “good” Δ indicates “no practical problem” × indicates “practical problem” ”Respectively.

[0152]

[Table 3]

[0153]

[Table 4] As is clear from Tables 3 and 4, the surface layer has silicon atoms,
By simultaneously containing a hydrogen atom, a carbon atom, an oxygen atom, a fluorine atom as a halogen atom and a boron atom as a Group III atom, it is excellent in any evaluation of white spots, scratches, image deletion, and black spots due to toner fusion. Results were obtained. Example 2 A light receiving member for electrophotography was produced in exactly the same manner as in Example 1. Comparative Example 9 A light receiving member for electrophotography was produced in exactly the same manner as in Comparative Example 1. Comparative Example 10 A light receiving member for electrophotography was produced in exactly the same manner as in Comparative Example 2. Comparative Example 11 An electrophotographic light-receiving member was produced in exactly the same manner as in Comparative Example 3. Comparative Example 12 An electrophotographic light-receiving member was produced in exactly the same manner as in Comparative Example 4. Comparative Example 13 An electrophotographic light-receiving member was produced in exactly the same manner as in Comparative Example 5. Comparative Example 14 An electrophotographic light-receiving member was produced in exactly the same manner as in Comparative Example 6. Comparative Example 15 A light receiving member for electrophotography was produced in exactly the same manner as in Comparative Example 7. Comparative Example 16 An electrophotographic light-receiving member was produced in exactly the same manner as in Comparative Example 8.

Example 2, Comparative Example 9, Comparative Example 10, Comparative Example 11, Comparative Example 12, Comparative Example 13, Comparative Example 14, Comparative Example 1
The photoreceptor for electrophotography prepared in Comparative Example 5 and Comparative Example 16 was used as copy paper for recycled paper (E-50, manufactured by Daishowa Paper).
0), the same evaluations as in Example 1 were performed.

“White spots”, “scratch”, “image deletion”,
Table 5 shows the results of the initial image before the endurance of “black spots due to toner fusion”, and Table 6 shows the results after the endurance of 2.5 million sheets.

[0156]

[Table 5]

[0157]

[Table 6] As is clear from Tables 5 and 6, even when recycled paper was used, Example 2 in which the surface layer simultaneously contained silicon atoms, hydrogen atoms, carbon atoms, oxygen atoms, fluorine atoms, and boron atoms was a comparative example. As compared with Nos. 9 to 16, good results were obtained particularly in any evaluation of white spots, scratches, image deletion, and black spots due to toner fusion after durability. Example 3 An electrophotographic light-receiving member was manufactured in the same manner as in Example 1 by using an apparatus for manufacturing an electrophotographic light-receiving member by the RF glow discharge method shown in FIG. The results were as good as in Example 1. Example 4 A photoreceptor for electrophotography was produced in the same manner as in Example 1 using the apparatus for producing a photoreceptor for electrophotography by the RF glow discharge method shown in FIG. When the same evaluation was made, good results were obtained as in Example 2.

[0158]

[Table 7] Example 5 Using the apparatus for manufacturing a photoreceptor for electrophotography by the μW glow discharge method shown in FIGS. 5 and 6, the diameter φ was mirror-finished under the manufacturing conditions shown in Table 8 according to the procedure described in detail above.
Form a light receiving layer on a 108 mm aluminum cylinder,
A light receiving member for electrophotography was produced. When the produced electrophotographic light-receiving member was evaluated in the same manner as in Example 1, good results were obtained. Example 6 An electrophotographic light-receiving member was produced in the same manner as in Example 5 by using the apparatus for producing an electrophotographic light-receiving member by the μW glow discharge method shown in FIGS. When the same evaluation as in Example 2 was performed, good results were obtained.

[0159]

[Table 8] Example 7 A light receiving layer was formed on a mirror-finished aluminum cylinder having a diameter of 108 mm by using the manufacturing apparatus based on the RF glow discharge method shown in FIG. The light receiving member 10 for electrophotography was formed. In this prototype, by changing the power introduced during the formation of the surface layer and the CH ₄ flow rate, the carbon atom content near the outermost surface of the surface layer was reduced by 70 to 70% of the sum of the silicon atom content and the carbon atom content. It was changed in the range of 90 atomic%. However, at this time, the carbon atom content on the surface of the surface layer on the side of the photoconductive layer was set to 10 atomic%.

[0160]

[Table 9] The produced electrophotographic light receiving member was transferred to a Canon copier N
P-7550 was installed in an electrophotographic apparatus modified for experiments, and image characteristics such as image deletion, white spots, black spots due to toner fusion, and flaws were evaluated. Also,
For this electrophotographic light-receiving member, 2
After 500,000 sheets of continuous paper image formation durability test, the above items were evaluated again.

[Comparative Example 17] The carbon atom content near the outermost surface of the surface layer was determined to be 20 to 60 atomic% and 93 to 95 atomic% with respect to the sum of the silicon atom content and the carbon atom content.
Light-receiving members for electrophotography were prepared in the same manner as in Example 7 except for the above, and evaluated in the same manner as in Example 7. Table 10 shows the evaluation results of Example 7 and Comparative Example 17 before the durability test. Table 11 shows the evaluation results of Example 7 and Comparative Example 17 after the durability test.

[0162]

[Table 10]

[0163]

[Table 11] From this evaluation result, the photoreceptor for electrophotography according to the present invention in which the carbon atom content in the vicinity of the outermost surface of the surface layer is in the range of 70 to 90 atomic% with respect to the sum of the silicon atom content and the carbon atom content It was found that the member provided good electrophotographic characteristics. [Embodiment 8] Using a manufacturing apparatus based on the μW glow discharge method shown in FIGS. A receiving layer was formed and a light receiving member for electrophotography was prepared in the same manner as in Example 7.

[0164]

[Table 12] Evaluation of the produced electrophotographic light-receiving member was performed in the same manner as in Example 7. The results were the same as in Example 7.

[Comparative Example 18] The carbon atom content near the outermost surface of the surface layer was determined to be 20 to 60 atomic% and 93 to 95 atomic% with respect to the sum of the silicon atom content and the carbon atom content.
Light receiving members for electrophotography were prepared in the same manner as in Example 8 except for the above. As a result of evaluation in the same manner as in Example 8, deterioration of characteristics was confirmed.

Ninth Embodiment Using a manufacturing apparatus based on the RF glow discharge method shown in FIG. 4, light was radiated on a mirror-finished aluminum cylinder having a diameter of 108 mm according to the conditions described in Table 13 according to the procedure described in detail above. A light receiving layer was formed to form a light receiving member for electrophotography. In this example, the oxygen content of the surface layer was changed in the range of 1 × 10 ⁻⁴ to 30 atom% by changing the flow rate of CO ₂ introduced during the formation of the surface layer.

[0167]

[Table 13] The produced electrophotographic light receiving member was transferred to a Canon copier N
P-7550 installed in an electrophotographic device modified for experiment, electrophotographic characteristics such as charging ability, sensitivity, residual potential, and image characteristics such as image deletion, white spots, black spots due to toner fusion, and scratches Each evaluation was performed in the same manner as in Example 7. The electrophotographic light-receiving member was evaluated again on the above items after a continuous paper image formation durability test of 2.5 million sheets using recycled paper.

Comparative Example 19 Light receiving members for electrophotography were prepared in the same manner as in Example 9 except that the oxygen content of the surface layer was changed to 1 × 10 ⁻⁵ atomic% and 40 to 50 atomic%. Then, evaluation was performed in the same manner as in Example 9. In Table 14,
19 shows the evaluation results of Example 9 and Comparative Example 19 before the durability test. Table 15 shows the evaluation results of Example 9 and Comparative Example 19 after the durability test.

[0169]

[Table 14]

[0170]

[Table 15] From this evaluation result, the oxygen content of the surface layer was 1 × 10
It has been found that the electrophotographic light-receiving member of the present invention in which the content is in the range of ^-4 to 30 atomic% can provide good electrophotographic properties.

[Embodiment 10] Using the manufacturing apparatus based on the μW glow discharge method shown in FIGS.
A light receiving layer was formed on an 08 mm aluminum cylinder, and a light receiving member for electrophotography was prepared in the same manner as in Example 9.

[0172]

[Table 16] Evaluation of the produced electrophotographic light-receiving member was performed in the same manner as in Example 9. The results were the same as in Example 9.

[Comparative Example 19] Light receiving members for electrophotography were prepared in the same manner as in Example 10 except that the oxygen content of the surface layer was changed to 1 × 10 ^-5 atomic% and 40 to 50 atomic%. did. As a result of evaluation in the same manner as in Example 10,
Deterioration of characteristics was confirmed.

[Embodiment 11] Using a manufacturing apparatus based on the RF glow discharge method shown in FIG. 4, a mirror-finished surface having a diameter of 108 mm
A light receiving layer was formed on an aluminum cylinder of No. 1 to prepare a light receiving member for electrophotography. In this prototype, the nitrogen content of the surface layer was changed in the range of 1 × 10 ⁻⁴ to 30 atom% by changing the flow rate of N ₂ introduced during the formation of the surface layer.

[0175]

[Table 17] The prepared electrophotographic photoreceptor member 10 is installed in an electrophotographic apparatus obtained by modifying a Canon copier NP-7550 for an experiment, and electrophotographic properties such as charging ability, sensitivity, and residual potential are set.
In addition, image characteristics such as image deletion, white spots, black spots due to toner fusion, and scratches were evaluated in the same manner as in Prototype Example 9. The electrophotographic light-receiving member was evaluated again on the above items after a continuous paper image formation durability test of 2.5 million sheets using recycled paper.

Comparative Example 21 Light receiving members for electrophotography were prepared in the same manner as in Example 11, except that the nitrogen content of the surface layer was changed to 1 × 10 ⁻⁵ atomic% and 40 to 50 atomic%. Then, evaluation was performed in the same manner as in Example 11. Table 18
9 shows the evaluation results of Example 11 and Comparative Example 21 before the durability test. Table 19 shows Example 11 and Comparative Example 2.
1 shows the evaluation results after the durability test.

[0177]

[Table 18]

[0178]

[Table 19] From this evaluation result, the nitrogen content of the surface layer was 1 × 10
It has been found that the electrophotographic light-receiving member of the present invention in which the content is in the range of ^-4 to 30 atomic% can provide good electrophotographic properties.

Example 12 Using a manufacturing apparatus based on the μW glow discharge method shown in FIGS. 5 and 6, a mirror surface having a diameter of 1
A light receiving layer was formed on an 08 mm aluminum cylinder, and a light receiving member for electrophotography was prepared in the same manner as in Example 11.

[0180]

[Table 20] Evaluation of the produced electrophotographic light-receiving member was performed in the same manner as in Example 11. The results were the same as in Example 11.

Comparative Example 22 Light receiving members for electrophotography were prepared in the same manner as in Example 12, except that the nitrogen content of the surface layer was 1 × 10 ⁻⁵ atomic% and 40 to 50 atomic%. did. As a result of performing evaluation in the same manner as in Example 12,
Deterioration of characteristics was confirmed.

Example 13 Using a manufacturing apparatus based on the RF glow discharge method shown in FIG. 4, a mirror-finished surface having a diameter of 108 mm
A light receiving layer was formed on an aluminum cylinder of No. 1 to prepare a light receiving member for electrophotography. In this prototype, by changing the flow rate of B ₂ H ₆ introduced when forming the surface layer,
The boron atom content used as a group III element is 1 × 10 ⁻⁵ to
It was changed in the range of 1 × 10 ⁵ atomic ppm.

[0183]

[Table 21] The produced electrophotographic light receiving member was transferred to a Canon copier N
P-7550 installed in an electrophotographic device modified for experiment, electrophotographic characteristics such as charging ability, sensitivity, residual potential, and image characteristics such as image deletion, white spots, black spots due to toner fusion, and scratches Evaluation was performed in the same manner as in Example 11. Further, regarding this electrophotographic light receiving member,
After a continuous image formation durability test of 2.5 million sheets using recycled paper, the above items were evaluated again.

Comparative Example 23 An electrophotographic light-receiving member was prepared in the same manner as in Example 13 except that the boron atom content of the surface layer was changed to 1 × 10 ⁻⁶ atomic ppm and 1 × 10 ⁶ atomic ppm. It was prepared and evaluated in the same manner as in Example 13. Table 22 shows the evaluation results of Example 13 and Comparative Example 23 before the durability test. Table 23 shows the evaluation results of Example 13 and Comparative Example 23 after the durability test.

[0185]

[Table 22]

[0186]

[Table 23] From this evaluation result, boron atoms (Group III elements) in the surface layer
It was found that the electrophotographic light-receiving member of the present invention in which the content was in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁵ atomic ppm could obtain good electrophotographic properties.

Example 14 Using a manufacturing apparatus based on the .mu.W glow discharge method shown in FIGS.
A light receiving layer was formed on an 08 mm aluminum cylinder, and a light receiving member for electrophotography was prepared in the same manner as in Prototype Example 13.

[0188]

[Table 24] The produced electrophotographic light-receiving member was evaluated in the same manner as in Example 13. The result was similar to that of Prototype Example 13.

Comparative Example 24 An electrophotographic light-receiving member was prepared in the same manner as in Example 14 except that the boron atom content of the surface layer was changed to 1 × 10 ⁻⁶ atomic ppm and 1 × 10 ⁶ atomic ppm. Created. As a result of evaluation in the same manner as in Example 14, deterioration in characteristics was confirmed.

[Embodiment 15] Using a manufacturing apparatus based on the RF glow discharge method shown in FIG. 4, a mirror-finished diameter of 108 mm
A light receiving layer was formed on an aluminum cylinder of No. 1 to prepare a light receiving member for electrophotography. In this prototype, the power introduced during the formation of the surface layer and the flow rate of SiF ₄ were changed to change the hydrogen atom content and the fluorine atom (used as halogen atom) content of the surface layer. The sum with the atomic content was adjusted to be 80 atomic% or less.

[0191]

[Table 25] The prepared electrophotographic photoreceptor member 10 is installed in an electrophotographic apparatus obtained by modifying a Canon copier NP-7550 for an experiment, and electrophotographic properties such as charging ability, sensitivity, and residual potential are set.
In addition, image characteristics such as image deletion, white spots, black spots due to toner fusion, and flaws were evaluated in the same manner as in Example 13. The electrophotographic light-receiving member was evaluated again on the above items after a continuous paper image formation durability test of 2.5 million sheets using recycled paper.

Comparative Example 25 Light receiving members for electrophotography were prepared in the same manner as in Example 15 except that SiF ₄ was not introduced at the time of forming the surface layer, and evaluation was performed in the same manner as in Example 15. . Table 26 shows Example 15 and Comparative Example 25.
2 shows the evaluation results before the durability test. Table 27 shows the evaluation results of Example 15 and Comparative Example 25 after the durability test.

[0193]

[Table 26]

[0194]

[Table 27] From this evaluation result, the electrophotographic light-receiving member of the present invention in which the surface layer contains a halogen atom and the sum of the hydrogen atom content and the boron atom (halogen atom) content is in the range of 80 atom% or less. It was found that good electrophotographic characteristics were obtained.

Example 16 Using a manufacturing apparatus based on the .mu.W glow discharge method shown in FIGS.
A light receiving layer was formed on an 08 mm aluminum cylinder, and a light receiving member for electrophotography was prepared in the same manner as in Example 15.

[0196]

[Table 28] Evaluation of the produced electrophotographic light-receiving member was performed in the same manner as in Example 15. The results were the same as in Example 15.

Comparative Example 26 Light receiving members for electrophotography were prepared in the same manner as in Example 16 except that SiF ₄ was not introduced during the formation of the surface layer. As a result of evaluation in the same manner as in Example 16, deterioration in characteristics was confirmed.

Example 17 Using a manufacturing apparatus based on the RF glow discharge method shown in FIG. 4, a mirror-finished surface having a diameter of 108 mm
A light receiving layer was formed on an aluminum cylinder of No. 1 to prepare a light receiving member for electrophotography. In this prototype, the sum of the oxygen content and the nitrogen content of the surface layer was changed from 1 × 10 ⁻⁴ to 30 by changing the NO flow rate introduced during the formation of the surface layer.
It was changed in the range of atomic%.

[0199]

[Table 29] The produced electrophotographic light receiving member was transferred to a Canon copier N
P-7550 installed in an electrophotographic device modified for experiment, electrophotographic characteristics such as charging ability, sensitivity, residual potential, and image characteristics such as image deletion, white spots, black spots due to toner fusion, and scratches Evaluation was performed in the same manner as in Example 15. Further, regarding this electrophotographic light receiving member,
After a continuous image formation durability test of 2.5 million sheets using recycled paper, the above items were evaluated again.

Comparative Example 27 The sum of the oxygen atom content and the nitrogen atom content of the surface layer was 1 × 10 ⁻⁵ atomic% and 40 to
Light receiving members for electrophotography were prepared in the same manner as in Example 17 except that the content was changed to 50 atomic%, and the evaluation was performed in the same manner as in Example 17. Table 30 shows Example 17 and Comparative Example 2.
7 shows the evaluation results before the durability test. Table 31 shows the evaluation results of Example 17 and Comparative Example 27 after the durability test.

[0201]

[Table 30]

[0202]

[Table 31] From these evaluation results, it was found that the electrophotographic light-receiving member 10 of the present invention in which the sum of the oxygen atom content and the nitrogen atom content of the surface layer was in the range of 1 × 10 ⁻⁴ to 30 atom%, showed good electrophotography. It was found that characteristics were obtained.

[Embodiment 18] Using the manufacturing apparatus based on the μW glow discharge method shown in FIGS.
A light receiving layer was formed on an 08 mm aluminum cylinder, and a light receiving member for electrophotography was prepared in the same manner as in Example 17.

[0204]

[Table 32] Evaluation of the produced electrophotographic light-receiving member was performed in the same manner as in Example 17. The results were the same as in Example 17.

[Comparative Example 28] The sum of the oxygen atom content and the nitrogen atom content of the surface layer was 1 × 10 ^-5 atom% and 40 to
Light receiving members for electrophotography were prepared in the same manner as in Prototype Example 18, except that the content was changed to 50 atomic%. Evaluation was performed in the same manner as in Prototype Example 18, and as a result, deterioration of the characteristics was confirmed.

[0206]

The light-receiving member for electrophotography according to the present invention has a layer structure as described above, and the surface layer has at least silicon atoms,
Hydrogen atom, carbon atom, halogen atom and Periodic Table II
By simultaneously containing a Group I element and an oxygen atom or a nitrogen atom, these synergistic effects are effective in reducing image defects such as "pots", especially in reducing "leak points" during long-term use, and further regenerate Extremely excellent image characteristics, durability, and usage environment characteristics are exhibited by preventing the occurrence of scratches when using paper and eliminating toner fusing and image deletion during long-term use.

[Brief description of the drawings]

FIG. 1 is a schematic layer configuration diagram for explaining a layer configuration of a preferred embodiment of an electrophotographic light-receiving member of the present invention.

FIG. 2 is a schematic layer configuration diagram for explaining a layer configuration of a preferred embodiment of the electrophotographic light-receiving member of the present invention.

FIG. 3 is a schematic layer configuration diagram for explaining a layer configuration of a conventional electrophotographic light receiving member.

FIG. 4 is an example of an apparatus for forming a light receiving layer of the electrophotographic light receiving member of the present invention, and is a schematic view of an apparatus for manufacturing an electrophotographic light receiving member by a glow discharge method using high frequency (RF). FIG.

FIG. 5 is another example of an apparatus for forming a light receiving layer of the electrophotographic light receiving member of the present invention, which is an apparatus for manufacturing an electrophotographic light receiving member by a glow discharge method using microwaves (μW). FIG. 3 is a schematic cross-sectional view of a deposited film forming apparatus.

6 is a cross-sectional view of the apparatus of FIG. 5 as viewed from above.

FIG. 7 is a source gas supply device.

[Explanation of symbols]

1100, 1200, 200 Light receiving member 1101, 1201, 201 Conductive support 1102, 1103, 1202, 1203, 202
Photoconductive layer 1104, 1204 Surface layer 1205 Charge injection blocking layer 1105, 1206 Light receiving layer 1106, 1207, 203 Free surface 3100 Deposition device 3111 Reaction vessel 3112 Cylindrical support 3113 Support heating heater 3114 Raw material gas introduction pipe 3115 Matching Box 3116 Source gas piping 3117 Reaction vessel leak valve 3118 Main exhaust valve 3119 Vacuum gauge 3200 Source gas supply device 3211 to 316 Mass flow controller 3221 to 226 Source gas cylinder 3231 to 236 Source gas cylinder valve 3241 to 246 Gas inflow valve 3251 to 256 Gas outflow valve 3261 to 3266 Pressure regulator 4100 Deposition device 4111 Reaction vessel 4112 Microwave introduction window 4113 Waveguide 411 Support holder 4115 cylindrical support 4116 supports heater 4117 source gas inlet pipe 4118 bias electrode 4119 bias power source 4120 support rotating motor 4121 exhaust pipe 4130 discharge space

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification code FI G03G 5/08 312 G03G 5/08 312 (56) References JP-A-64-40840 (JP, A) JP-A-3-107863 (JP, A) JP-A-1-173050 (JP, A) JP-A-5-181296 (JP, A) Patent 2960609 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 5/08

Claims (6)

(57) [Claims] 1. A photoreceptor member comprising: a photoconductive layer and a surface layer each formed of a non-single-crystal material having silicon atoms as a matrix on a conductive support, wherein the photoconductive layer is composed of silicon atoms , composed of a hydrogen atom or a halogen atom
And the surface layer is composed of silicon atoms, carbon atoms, and hydrogen atoms.
Or a halogen atom, a periodic table Group III element, with further contains oxygen atoms or nitrogen atoms, the outermost
The content of carbon atoms on the surface or near the outermost surface is
70 atom% or more based on the sum of silicon atoms and carbon atoms,
A light receiving member having a content of 90 atomic% or less . 2. A surface layer, a hydrogen atom, a halogen atom, light-receiving member according to claim 1, characterized in that it contains an oxygen atom and a nitrogen atom at the same time. The content of 3. oxygen atoms and / or nitrogen atoms of the surface layer is, the light receiving member according to claim 1 or 2, characterized in that 1 × 10 ^-4 ~ 30 atomic% or less . 4. A sum of the content of hydrogen atoms and halogen atoms in the surface layer is, in any one of claims 1 to 3, characterized in that 1 × 10 ^-5 ~ 80 atomic% or less The light receiving member according to any one of the preceding claims. Content of 5. periodic table Group III element of the surface layer is, the light according to any one of claims 1 to 3, wherein not more than 1 × 10 ⁵ atomic ppm Receiving member. 6. The photoconductive layer according to claim 3, further comprising :
A group or group V element is contained.
The light receiving member according to any one of claims 1 to 5.