JPH08262753A - Electrophotographic photoreceptive member - Google Patents

Abstract

PURPOSE: To easily obtain a photoreceptive member ensuring very few image defects difficult to attain so far even by strict production in an environment having high cleanness without producing side effects such as the blurring of an image and the lowering of sensitivity. CONSTITUTION: At least the top part of this photoreceptive member 100 is made of an amorphous material contg. silicon atoms and regions 105 in which a transition metal exists and a region 106 in which the transition metal does not, practically exist are two-dimensionally distributed on the surface of this photoreceptive member.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In the field of image formation, a photoconductive material forming a light-receiving layer of a light-receiving member for electrophotography has a high sensitivity and S
It has a high N ratio, has absorption spectral characteristics that match the spectral characteristics of the electromagnetic waves that it irradiates, and has a fast photoresponsiveness.
Various characteristics such as having a desired dark resistance value and being non-polluting to the human body during use are required. Amorphous silicon (hereinafter referred to as A-Si) is a photoconductive material that satisfies these requirements, and its application is described, for example, in JP-A-54-86341 as a light receiving member for electrophotography.

Further, Japanese Patent Application Laid-Open No. 57-11556 discloses a photoconductive member having a photoconductive layer formed of an A-Si deposited film, which has electrical properties such as dark resistance, photosensitivity and photoresponsiveness. In order to improve the use environment characteristics such as optical and photoconductive characteristics and moisture resistance, and further the stability over time, silicon atoms and carbon are formed on the photoconductive layer composed of an amorphous material with silicon atoms as a base material. A technique for providing a surface barrier layer composed of a non-photoconductive amorphous material containing atoms is described.

Further, Japanese Patent Application Laid-Open No. 60-67951 discloses a technique relating to a photoconductor in which a translucent insulating overcoat layer containing A-Si, carbon, oxygen and fluorine is laminated. . Also, JP-A-62-168161
The publication describes a technique of using, as the surface layer, an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% hydrogen atoms as constituent elements. JP 59-1
No. 02239 discloses a Friedel-Crafts catalyst with A-
Techniques for treating the surface of a Si-based photoreceptor have been disclosed.
Further, Japanese Patent Application Laid-Open No. 59-102240 discloses A-Si.
A technique of treating the surface of a photoconductor with an organometallic compound is disclosed.

In Japanese Patent Laid-Open No. 61-231558, image flow characteristics are obtained by mechanically removing at least a part of a solid-phase reaction product generated by contacting a surface of an electrophotographic photoreceptor with a metal which causes a solid-phase reaction. A technique for significantly improving the above is disclosed. JP-A-60-28658 discloses that A-Si containing metal atoms and / or metal ions.
A surface protective layer of a system is disclosed, and as the metal, Group IIIb, Group IVb, Group Vb, Group VIb of the periodic table are used.
Mention is made of transition metals belonging to Group VIIb, Group VIII, Group Ib or Group IIb and the metals constituting the Friedel-Crafts catalyst. Furthermore, JP-A-1-24612
No. 0 discloses an A-Si film containing a divalent metal element such as magnesium or calcium.

By the way, in recent years, there is an increasing demand for higher image quality of images formed by electrophotographic apparatuses. In order to meet this demand, for example, in the developing process, a technique for improving the image quality such as reducing the particle diameter of the toner has been proposed. As a result of the development of such an image quality improving technique, a defect that has not been a problem up to now has become a problem with an electrostatic latent image. A particular problem in the defect of the electrostatic latent image is the nonuniformity of the spot-like surface potential due to the defect of the light receiving member forming the electrostatic latent image. Such non-uniformity of the surface potential appears as white spots on the black image due to the positive development process and as black spots on the white image during reversal development.

In the case of an electrophotographic light-receiving member containing a layer made of A-Si, if any foreign matter adheres to the support used during the formation of the deposited film in the production of the same, the light-receiving member will be damaged. It has been conventionally known that an image formed by use of the above-described image has image defects due to the above-mentioned foreign matter.
Conventionally, in order to prevent foreign matters from adhering to the support during the handling of the support before the formation of the deposited film, thorough countermeasures against particles have been taken. However, in the case of a photoreceptive member for electrophotography, if there is a defect in one place on a copy image formed using the electrophotographic light-receptive member, no matter how good the image may be on the other part, it will be a commercial product. There was a circumstance that the value was lost, and it was necessary to have a high degree of cleanliness when handling the support compared to other devices. Then, as the required image quality becomes higher, the required cleanliness level becomes higher, and finally, the cleanliness level at the time of manufacturing the ultra-high density semiconductor device is always required. It is technically difficult to maintain such cleanliness and it is a heavy burden on the cost. Further, in spite of such cleanliness, the present situation is that the image quality of the produced light-receiving member and the yield at the time of production are not satisfactory at all. As described above, there is room for improvement even in the conventional electrophotographic light-receiving member.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve various problems in the electrophotographic light-receiving member having the conventional light-receiving layer composed of A-Si as described above. . That is, the main object of the present invention is a photoreceptive member for electrophotography, which has a dramatically improved image quality, and in particular, the number of image defects is as near to zero as possible, which is low in cost and good in productivity, electrical and optical. An object of the present invention is to provide a photoreceptive member for electrophotography, which has excellent characteristics and good durability, and at least a part of which is made of an amorphous material containing silicon atoms.

[0009]

The electrophotographic light-receiving member of the present invention is made of a non-single crystalline material containing at least the outermost surface portion of a silicon atom, and is formed on a part of the outermost surface of the electrophotographic light-receiving member. At least one metal atom selected from transition metals is present, and a region where the metal atom exists and a region where the metal atom does not substantially exist are two-dimensionally distributed on the outermost surface. . The electrophotographic light-receiving member of the present invention designed to have the above-mentioned configuration solves all of the above-mentioned problems, and can dramatically obtain high-quality images with few defects, It is characterized by being able to obtain high productivity at a very low cost during production.

The present inventors have found the above as a result of detailed examination of the electrophotographic light-receiving member itself in order to overcome the problems of the prior art. That is, the inventors of the present invention initially investigated the improvement of cleanliness at the manufacturing site in order to obtain a high-quality image electrophotographic light-receiving member with few image defects. However, as the required image quality rises, it is necessary to improve the class of the clean room, and the image quality and yield cannot be sufficiently satisfied with the demands of the times. Therefore, the present inventors have improved the electrophotographic light-receiving member itself,
The study was conducted from the viewpoint of being able to eliminate image defects fundamentally.

Prior to this study, the present inventors conducted a study to clarify the mechanism of why an image defect occurs. In the conventional electrophotographic light-receiving member, the position of the light-receiving member surface corresponding to the image defect on the copy image was observed with a microscope, and as a result, a substantially circular protrusion having a diameter of 20 to 50 μm as a center (hereinafter, “ (Referred to as "spherical projections"). When the structure was confirmed by cutting the cross section of the spherical protrusion, there was a foreign substance of about several μm in the vicinity of the support, and abnormal growth of the deposited film occurred in an inverted conical shape with this foreign substance as a nucleus. On the other hand, image defects on the copy image corresponding to these spherical protrusions were confirmed as white spots having a diameter of about 0.1 mm to 0.5 mm, and surprisingly did not match the size of the spherical protrusions at all.

Next, in order to clarify the cause of the contradiction, the present inventors conducted a normal electrophotographic process with an electrophotographic apparatus, placed toner on the light receiving member, and formed a toner image. The process was stopped, the light receiving member was taken out, and the toner image before transfer formed on the light receiving member was observed with a microscope. As a result, it was discovered that there is a substantially circular portion on the surface of the light receiving member around the spherical protrusion, on which the toner is not attached.

Usually, the spherical projection has a diameter of about 20 to 50 μm. On the other hand, the image defects that can be confirmed with the naked eye of the copied image are 0.1 mm to 0.2 mm or more. Even if the toner does not adhere to the spherical protrusions, it should be impossible to easily recognize white spots of this size on the image. In other words, even a spherical protrusion of this size may appear as an image defect on the image, which makes the production of the electrophotographic light-receiving member using A-Si much more difficult than production of other materials. It was the root cause of demanding a high degree of cleanliness.

These phenomena have many unclear points as a mechanism. At the present time, the present inventors consider as follows. That is, the spherical protrusion grows in an inverted conical shape with a foreign substance such as dust as a nucleus. The interface between the spherical projection and the normal film is a contact point for different growth, and the dangling bonds are essentially present at high density and have low electrical resistance. Since the electrostatic charge charged on the surface of the photoconductor passes through the low resistance portion and escapes to the substrate, there is a portion having a low surface potential even after the charging.

On the other hand, the density of the spherical projections and the growth rate are different from those of the normal deposited film. That is, the spherical protrusion grows so as to push the surrounding deposited film. Therefore, strong mechanical forces act on each other at the interface between the spherical protrusion and the ordinary deposited film. As a result, the deposited film around the spherical protrusion is subjected to a very large stress, especially in the vicinity of the surface layer. Since a high-quality A-Si film causes band bending due to such stress, it has a low resistance to holes, and a lateral charge flow occurs when a positive electric field is applied. The electrostatic charge charged on the deposited film around the spherical projections causes a lateral flow first by such a process, gathers on the spherical projections, and then escapes to the support. The conventional approach has been to reduce the incidence of spherical protrusions by taking thorough countermeasures against particles, but it is essentially impossible to eliminate image defects unless the lateral flow of charges due to this stress is essentially stopped. It is the conclusion of the present inventors that it is extremely difficult.

As a result of intensive studies on the method of reducing the band bending spread around the spherical projections, the present inventors have found that in a positively charged photoreceptor member for electrophotography, a metal having a plurality of valences is present on the photoreceptor surface. It has been found that attaching atoms is effective. This effect was especially remarkable in the case of transition metals. That is, a metal atom having a plurality of valences behaves as a so-called donor impurity element and supplies an electron to A-Si. Therefore, the Fermi level in the vicinity of the outermost surface of the light receiving member in contact with such metal atoms is increased, and as a result, the band bending in the vicinity of the surface is reduced. However, when the metal is added to the surface to such a level that the image defects are sufficiently reduced, that is, there is substantially no toner-free area around the spherical projection, the charged electric charge is again caused by the high conductivity of the metal itself. The image flow occurs due to the deposition of metal atoms, which starts the lateral flow.

The inventors of the present invention have made it possible for the metal atom to adhere to the surface of the light-receiving member to reduce band bending around the spherical protrusion and to prevent image deletion due to the conductivity of the metal atom itself, so that the optimum amount of metal atom attachment is obtained. As a result of diligent examination of the attachment form, an electrophotographic light-receiving member having a structure in which a region where metal atoms are present and a region where metal atoms are not substantially present are two-dimensionally distributed on the outermost surface of the light-receiving member. We obtained the finding that the purpose can be achieved by using it. That is, in order to alleviate the band bending due to the stress of the spherical projection, it is necessary to allow relatively high density metal atoms to exist near the surface, but when using a transition metal as the metal atom,
It was found that it is not necessary to contain the light-receiving member over the entire surface, and if there is a locally-containing portion, the band bending can be alleviated to a level where there is no problem on the image. Further, the two-dimensional distribution can effectively prevent the lateral movement of the charged electric charges, and eliminate the side effect of image deletion.

Considering the two-dimensional distribution state of metal atoms, which has not been taken into consideration in the past, a large amount of metal atoms, which was not possible in the past, was contained on the surface of the light receiving member without deteriorating various physical properties. Is an achievement of the present inventors. That is, according to the present invention, a region in which metal atoms are present and a region in which metal atoms are not substantially present are two-dimensionally distributed, which is very effective in preventing image defects without impairing electrophotographic characteristics. A light receiving member for electrophotography was completed. In addition, since a large amount of metal atoms, which has not been considered before, can be made to exist, the life of metal atoms is dramatically extended, and the effect of the present invention is extended semipermanently (to the same level as the life of the main body of an electrophotographic device). It has become possible.

In the present invention, it is more effective to use SiC for the surface layer. That is, when the surface material is SiC, the hardness, wear resistance, and moisture resistance originally possessed by SiC are drastically extended, and at the same time, the action of the present invention is effectively exhibited and the effect is more remarkable. You can now get to.

The light receiving member of the present invention will be described in detail below with reference to the drawings. 1 to 4 are schematic explanatory views for explaining the layer structure of the electrophotographic light-receiving member of the present invention.

FIG. 1 shows an example of the electrophotographic light-receiving member of the present invention. In the electrophotographic light-receiving member 100, a light-receiving layer 102 is provided on a support 101 for the light-receiving member. The light receiving layer 102 is made of A-Si (H, X).
And a photoconductive layer 103 having photoconductivity. In the photoconductive layer 103, a region 105 in which metal atoms are present on the outermost surface on the side opposite to the support, and a region 106 in which the metal atoms are substantially absent are two-dimensionally distributed in other regions.

FIG. 2 shows a light receiving layer 102 on a support 101.
1 has the same layer structure as that shown in FIG. 1, but is another example of the electrophotographic light-receiving member of the present invention in which metal atoms are present on the surface in a shape different from that shown in FIG. .
3 and 4 are the same as those shown in FIGS. 1 and 2 in the layer structure in which the light receiving layer 102 is provided on the support 101, but the metal of the one shown in FIGS. This is an example in which metal atoms are attached in a larger amount than the atomic weight. in this case,
This is an example of a light receiving member for electrophotography having a two-dimensional distribution of regions 106 in which metal atoms are substantially absent in regions 105 in which metal atoms are present.

FIG. 5 is a schematic explanatory view for explaining another layer structure of the light receiving member for electrophotography of the present invention. Figure 5
In the electrophotographic light-receiving member 100 shown in (1), a light-receiving layer 102 is provided on a support 101 for the light-receiving member. The light receiving layer 102 is made of A-Si (H, X), and is composed of a photoconductive layer 103 having photoconductivity and an A-Si based surface layer 104. The surface layer 104 has a two-dimensional distribution of regions 105 where metal atoms are present on the surface and regions 106 where metal atoms are substantially absent. In the case of FIG. 5 as well, it goes without saying that metal atoms may be present on the surface of the light receiving member in the shapes shown in FIGS.

[0024]

[Surface metal atom] In the present invention, a transition metal is present on the outermost surface of the light-receiving member produced as described above, and a region where the metal atom is present and substantially no metal atom is present. The regions are two-dimensionally distributed. Any structure is effective as long as the transition metal is two-dimensionally distributed on the outermost surface. As shown in FIGS. 1 and 2, a region where metal is present in a region where metal is substantially absent is Structures scattered in islands, structures where metal is substantially absent in regions where metal is present as shown in FIGS. 3 and 4, regions where metal is present in a mosaic, A configuration in which regions in which metal atoms are substantially absent are mixed is included. Among them, the structure shown in FIG. 1 and FIG. 2 in which the region where the metal is present is scattered like islands in the region where the metal is not substantially present effectively exhibits the effect of the present invention, and exhibits the side effect. Not desirable as a configuration.

The inventors of the present invention determined the ratio of the region where the metal atom exists, the diameter of the region where the metal atom exists, and the interval from the results of Experiments 1 to 5 described later. That is, as the ratio of the region where metal atoms are present and the region where metal atoms are not substantially present in the present invention, the region where metal is present is preferably 5% or more and 60% or less, more preferably 10% or more and 50%. The effects of the present invention are remarkably exhibited in the following ranges.

In the case where the region where the metal is present is scattered like islands in the region where the metal is not substantially present,
The size of the area where the metal is present is 200 Å or more and 5000 Å if the diameter or major axis is approximate to a circle or an ellipse.
Hereafter, it is more preferably 500 Å or more and 2000 Å or less. In addition, in the case where a pond-shaped metal atom does not exist in the region where the metal atom exists, the size of the region where the metal atom does not exist is 2000 Å or more and 8000 Å or less, more preferably 3000 Å or more and 5000 Å or less Is. If the distribution of the presence of metal atoms deviates from the above range, any adverse effect will occur on the properties of the surface layer of the electrophotographic light-receiving member, such as strength, transparency, durability, weather resistance and image deletion.

In the present invention, the transition metal contained on the surface is a group Ib, a group IIb or a group IIIa of the periodic table.
Group, Group IVa, Group Va, Group VIa, Group VIIa
At least one element selected from Group III and Group III is mentioned. In particular, at least one element selected from a main transition element, a lanthanoid element, and an actinoid element is included.

As the main transition element, specifically, scandium (Sc), titanium (Ti), zirconium (Z
r), vanadium (V), niobium (Nb), chromium (C
r), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver ( Examples thereof include Ag), gold (Au) and zinc (Zn). Specific examples of the lanthanoid element include lanthanum (La) and cerium (Ce), and specific examples of the actinoid element include actinium (Ac). Further, in the present invention, in addition to the above-mentioned atoms, any other atom may be contained as long as it is in a trace amount (1 atom% or less).

In the present invention, the method of attaching metal atoms to the surface of the light receiving member must be carefully selected so that the metal atoms easily condense on the surface into islands. For example, by strictly adjusting the conditions such as the plasma CVD method and sputtering, the metal atoms are provided with energy enough to obtain sufficient surface mobility in advance, and the metal atoms move when they reach the surface of the light receiving member. There is a method of facilitating and locally depositing there. Also,
There is a method in which a thin film of metal atoms is formed in a film shape on the surface of the light receiving member in advance by CVD, vacuum deposition, coating, or the like, and then thermal annealing is performed to condense the film surface into islands. In addition, plasma CVD method, sputtering, CV
A method is also suitable in which the substrate temperature is sufficiently raised in advance when performing D, vacuum vapor deposition, coating, etc., and the substrate temperature, pressure, vapor deposition time, etc. are controlled, and condensation is performed simultaneously with vapor deposition. In this case, if the substrate is heated for a too long time, the terminator such as hydrogen or halogen may be desorbed from the photoconductive layer and the characteristics may be deteriorated. Therefore, it is desirable to perform the vapor deposition time as short as possible.

Furthermore, ion implantation, sputtering,
Examples include a method of locally depositing a metal film using a mask by plasma CVD, plasma spraying, or the like, a method of locally implanting metal ions, and the like.

As other methods, a method of promoting local deposition by simultaneously or alternately performing deposition and etching, a method of preliminarily uniformly depositing and locally removing with an ion beam, and the like, conversely, an ion beam And a method of locally vapor-depositing. Alternatively, metal atoms may be attached to the front surface of the light receiving member and then the metal atoms attached to the convex portions may be scraped off by polishing.

In particular, when a thin film is formed by vapor deposition or the like, in the initial stage of formation of the deposited film, the deposited film is not uniformly formed, and a singular point on the substrate (attracting to active species moving on the substrate is attracted). Point) is used locally,
An island-shaped distribution can be easily obtained. Furthermore, if you want to obtain a high-concentration distribution of metal atoms, the island-shaped distribution obtained as described above is used as a nucleus, and then deposited film formation and etching or sputtering are performed simultaneously or alternately, The method of selectively forming a metal film only on the core portion has been successful in distributing a relatively large amount of metal in an island shape. For example, if you want to obtain a high concentration of metal atoms that are relatively difficult to be etched into islands, use the three-dimensional structure of the island itself after forming islands of metal atoms that will serve as nuclei on the surface of the deposited film by ordinary vapor deposition. Then, by simultaneously forming a film by introducing metal atoms from an oblique direction and removing the film by sputtering from a vertical direction, it is possible to effectively grow islands while leaving a localized distribution. Is possible.

The metal vapor deposition apparatus shown in FIG. 8 is used to form the metal film on the surface of the light receiving layer so that the regions containing the metal atoms have a two-dimensional distribution. The metal thin film is formed using the vacuum vapor deposition apparatus shown in FIG. 8 as follows. First, a vacuum pump (not shown) evacuates the vacuum container 801 through the exhaust pipe 808, and the pressure in the vacuum container 801 is adjusted to 1 × 10 ⁻⁷ Torr or less.
Therefore, the crucible 802 containing the metal raw material 803 is heated,
A metal vapor stream 804 is generated. During the formation of the metal thin film, the temperature of the support 805 is heated and maintained at a predetermined temperature by the heater 806 as necessary. Further, in the case of a cylindrical substrate, it is possible to deposit a metal thin film on the entire surface of the support 805 by rotating the rotary shaft 807. At this time, the substrate temperature, pressure, vapor deposition rate, vapor deposition time, etc. are controlled so that the vapor deposited metal film has a two-dimensional distribution.

[0034]

[Support] As the support used in the present invention,
It may be electrically conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au, In, Nb, Te,
Examples thereof include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Also, at least the surface of the electrically insulating support such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, or the like, on which the light receiving layer is formed, of the electrically insulating support such as glass or ceramic. It is also possible to use a support obtained by conducting a conductive treatment.

The shape of the support 101 used in the present invention may be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface. Further, the thickness thereof can be appropriately determined so that the electrophotographic light-receiving member 100 can be formed as desired, but when flexibility as the electrophotographic light-receiving member 100 is required, a support is used. It can be made as thin as possible within a range in which the function of 101 can be sufficiently exhibited. However, the support 101 is usually 10 μm in terms of manufacturing and handling, mechanical strength and the like.
That is all.

In particular, when image recording is performed using coherent light such as laser light, in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in a visible image, the surface of the support 101 is removed. You may provide unevenness in.
The unevenness of the surface of the support 101 is described in JP-A-60-168156.
No. 60-178457, No. 60-225.
It is created by a known method described in Japanese Patent Publication No. 854.

Further, as another method for more effectively eliminating the image defect due to the interference fringe pattern when the coherent light such as laser light is used, the surface of the support 101 is provided with a concavo-convex shape by a plurality of spherical trace depressions. It may be provided. That is, the support 1
The surface of No. 01 has unevenness smaller than the resolving power required for the electrophotographic light-receiving member 100, and the unevenness is due to a plurality of spherical trace depressions. Unevenness due to a plurality of spherical trace dents on the surface of the support 101 is disclosed in JP-A-61-231.
It is prepared by a known method described in Japanese Patent No. 561.

[0038]

[Photoconductive layer] In the present invention, a light receiving layer 102 is formed on a support 101 to effectively achieve its purpose.
The photoconductive layer 103 constituting a part of the above is formed by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so that desired characteristics can be obtained. Specifically, for example, a glow discharge method (low frequency CVD method, high frequency CV
AC discharge CVD method such as D method or microwave CVD method,
Or DC discharge CVD method), sputtering method, vacuum deposition method, ion plating method, photo CVD method, thermal C
It can be formed by various thin film deposition methods such as the VD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, load level under capital investment, manufacturing scale, and desired characteristics of the electrophotographic light-receiving member to be prepared. The glow discharge method, the sputtering method, and the ion plating method are preferable because it is relatively easy to control the conditions for producing a photoreceptive member having characteristics. These methods may be used together in the same system.

The substances that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ , and Si ₃ H.
Silicon hydrides (silanes) in a gas state such as ₈ and Si ₄ H ₁₀ or capable of being gasified may be mentioned. Further, SiH ₄ , S in terms of easiness of handling at the time of layer formation and good Si supply efficiency.
i ₂ H ₆ is preferred. In addition, these raw material gases for supplying Si may be added with H ₂ , He, A
It may be diluted with a gas such as r or Ne before use.

In the present invention, it is necessary for the photoconductive layer 103 to contain hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves layer quality, particularly This is because it is essential for improving photoconductivity and charge retention characteristics. The content of hydrogen atoms or halogen atoms, or the amount of the sum of hydrogen atoms and halogen atoms is 1 to 40 atom%, more preferably 3 to 35 atom% with respect to the sum of silicon atoms and hydrogen atoms and / or halogen atoms. Optimally 5 to 30 atom%
Is desirable.

To control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 103, for example, the temperature of the support 101, the raw material used for containing hydrogen atoms and / or halogen atoms The amount of the substance introduced into the reaction container, the discharge power, etc. may be controlled. In order to more easily control the introduction ratio of hydrogen atoms introduced into the photoconductive layer 103 to be formed, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is mixed with these gases to form a layer. It is preferably formed. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio.

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

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

It is also effective that the photoconductive layer contains carbon atoms and / or germanium atoms and / or oxygen atoms and / or nitrogen atoms. The content of carbon atom and / or germanium atom and / or oxygen atom / and / or nitrogen atom is preferably 0.00001 to 50 atom% with respect to the sum of silicon atom, carbon atom, germanium atom, oxygen atom and nitrogen atom, More preferably 0.0
1 to 40 atomic%, optimally 1 to 30 atomic% is desirable.
Carbon atoms and / or germanium atoms and / or oxygen atoms and / or nitrogen atoms may be evenly and uniformly contained in the photoconductive layer, or the content may change in the layer thickness direction of the photoconductive layer. There may be a portion having a non-uniform distribution.

Further, in the present invention, the photoconductive layer 103
It is preferable to contain an atom for controlling conductivity as necessary. Atoms that control conductivity are photoconductive layer 10
3 may be contained in a state of being uniformly distributed evenly in 3, or there may be a portion containing in an uneven distribution state in the layer thickness direction. The content of the atoms controlling the conductivity contained in the photoconductive layer 103 is preferably 1 × 10 ^{−3 to} 5 × 10 ⁴ atomic ppm, more preferably 1 × 10 ⁻² to 1 × 10 ⁴ Atomic ppm, optimally 1x
It is desirable that the concentration be 10 ^{−1 to} 5 × 10 ³ atomic ppm.

As the atom for controlling the above-mentioned conductivity, there is a so-called impurity in the field of semiconductors, and an atom belonging to Group IIIb of the periodic table which gives a p-type conduction characteristic (hereinafter referred to as “Group IIIb atom”). Or an atom belonging to Group Vb of the periodic table (hereinafter abbreviated as “Group Vb atom”) that imparts n-type conductivity can be used. Specific examples of the group IIIb atom include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl), and B, Al, and Ga are particularly preferable. . As the group Vb atom,
Specifically, phosphorus (P), arsenic (As), antimony (S)
b), bismuth (Bi), etc., and P and As are particularly preferable. In order to introduce these atoms structurally, the raw material for introducing the group IIIb atom or the raw material for introducing the group Vb atom in a gas state in the reaction vessel is added to the photoconductive layer 103 during the layer formation. It may be introduced together with other gas for forming.

Raw material for introducing group IIIb atoms
Is a raw material for introducing a group Vb atom.
Is a gas at room temperature and atmospheric pressure, or at least a layer forming condition
It is desirable that those that can be easily gasified under
Yes. As a raw material for introducing such a Group IIIb atom
In the present invention, the boron atom conductor is effectively used.
B is required₂H₆, B_FourH_Ten, B_FiveH₉, B_FiveH₁₁, B
₆H_Ten, B₆H₁₂, B₆H₁₄Such as boron hydride, BF₃, B
Cl₃, BBr₃Such as boron halides
It In addition, AlCl₃, GaCl₃, Ga ( CH₃)₃,
InCl₃, TlCl₃And so on.

In the present invention, a raw material for introducing a group Vb atom is effectively used. For introducing a phosphorus atom, phosphorus hydride such as PH ₃ , P ₂ H ₄ or PH ₄ I, P is used.
F ₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , P
Examples thereof include phosphorus halides such as I ₃ . In addition, As
_{H 3, AsF 3, AsCl 3} , AsBr 3, AsF 5, Sb
H ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , Bi
H ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a Group Vb atom. In addition, these raw material substances for atom introduction for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar, or Ne as needed before use.

In the present invention, the layer thickness of the photoconductive layer 103 is appropriately determined in accordance with the desire in view of obtaining desired electrophotographic characteristics and economical effects, but is preferably 3 to 120 μm, and more preferably Is 5-100μ
m, most preferably 10 to 80 μm.

In order to form the photoconductive layer 103 having the characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the support 101 and the gas pressure in the reaction vessel as desired. The temperature (Ts) of the support 101 is appropriately selected according to the layer design, but in the normal case, it is preferably 20 to 500 ° C., more preferably 50 to 480.
It is desirable to set the temperature to 100 ° C, optimally 100 to 450 ° C. Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, but in the normal case, it is preferably 1
× 10 ^{-5 to} 100 Torr, more preferably 5 × 10 ^-5
-30 Torr, optimally 1 * 10 < ^-4 > ^-10 Torr is preferable. In the present invention, the support temperature for forming the photoconductive layer and the above-mentioned ranges are mentioned as desirable numerical ranges of the gas pressure, but the conditions are not usually independently determined separately, and may be desired. It is desirable to determine the optimum value based on the mutual and organic relationships so as to form the light receiving member having the characteristics of.

In the light receiving member of the present invention, at least aluminum atoms, silicon atoms, hydrogen atoms and / or halogen atoms are contained in a non-uniform distribution state in the layer thickness direction on the support 101 side of the light receiving layer 102. It is desirable to have a layer region that does. Further, in the electrophotographic light-receiving member of the present invention, for the purpose of further improving the adhesiveness between the support 101 and the photoconductive layer 103, for example, Si ₃
An adhesion layer made of an amorphous material containing at least one of N ₄ , SiO ₂ , SiO, hydrogen atoms and halogen atoms, at least one of nitrogen atoms and oxygen atoms, and silicon atoms may be provided. A charge injection blocking layer may be provided for the purpose of blocking the injection of charges from the support. Further, a light absorption layer may be provided to prevent light interference.

[0052]

[Surface Layer] In the present invention, A- is further formed on the photoconductive layer 103 formed on the support 101 as described above.
It is also possible to form the Si-based surface layer 104. This surface layer 104 has a free surface 106, which is mainly moisture resistant,
Continuous repeated use characteristics, electrical pressure resistance, usage environment characteristics,
It is provided to achieve the object of the present invention in durability. Further, in the present invention, since each of the amorphous materials forming the photoconductive layer 103 and the surface layer 104 forming the light receiving layer 102 has a common constituent element of silicon atom, at the stacking interface. Ensuring chemical stability is sufficient. In the present invention, the method of forming the surface layer 104, the raw material gas, etc. can be basically the same as the method of forming the photoconductive layer, and the raw material gas can be used as it is. Is particularly preferred.

The material of the surface layer used in the present invention may be any amorphous material containing silicon, but a compound with a silicon atom containing at least one element selected from carbon, nitrogen and oxygen is preferable, and particularly, S
It is preferable to use iC as a main component. In the case of SiC, the amount of carbon is 30% with respect to the sum of silicon atoms and carbon atoms.
To 90% is preferred.

In the present invention, it is necessary that the surface layer 104 contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms,
This is because it is essential to improve the layer quality, particularly dark resistance and charge retention characteristics. The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms is set to 41 atom% or more and 71 atom% or less with respect to the sum of silicon atoms and hydrogen atoms and / or halogen atoms. desirable.

That is, it is known that defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer adversely affect the characteristics as a light receiving member for electrophotography. For example, the deterioration of the charging characteristics due to the injection of electric charges from the free surface, the fluctuation of the charging characteristics due to the change of the surface structure under the usage environment, for example, high humidity. This adverse effect is caused by the injection of electric charges and the trapping of the electric charges in the defects in the surface layer, thereby causing an afterimage phenomenon during repeated use.

However, if the hydrogen content in the surface layer is 41
By controlling to over atomic%, the defects in the surface layer will be greatly reduced, and as a result all of the above problems will be solved, and a dramatic improvement in electrical characteristics and high-speed continuous usability will be achieved compared to the conventional one. You can On the other hand, when the hydrogen content in the surface layer is 71 atomic% or more, the hardness of the surface layer decreases, and the surface layer cannot withstand repeated use. Therefore, controlling the hydrogen content in the surface layer to be within the above range is one of the very important factors in obtaining the desired electrophotographic properties that are remarkably excellent. The hydrogen content in the surface layer can be controlled by the flow rate of H ₂ gas, the support temperature, the discharge power, the gas pressure and the like.

Gas for supplying carbon used in the present invention
Possible substances are CH_Four, C₂H ₆, C₃H₈, C_Four
H_TenHydrocarbons in the gas state, such as
It can be cited as one that can be used effectively, and when further layers are created
CH in terms of ease of handling and good Si supply efficiency_Four,
C₂H₆Are preferred. Also these
C as a raw material gas for supplying H if necessary₂, He, A
It may be diluted with a gas such as r or Ne before use.

The substances that can be used as the gas for supplying nitrogen or oxygen used in the present invention include NH ₃ , NO and N _2.
The compounds in a gas state such as O, NO ₂ , H ₂ O, O ₂ , CO, CO ₂ , N ₂ or the like that can be gasified are mentioned as being effectively used. In addition, these raw material gases for supplying nitrogen and oxygen may be diluted with a gas such as H ₂ , He, Ar, and Ne as needed before use.

The carbon atom and / or the oxygen atom and / or the nitrogen atom may be uniformly contained in the surface layer, or may be nonuniform so that the content varies in the thickness direction of the surface layer. There may be a portion with a distribution.

Further, in the present invention, it is preferable that the surface layer 104 contains atoms for controlling the conductivity, if necessary. Atoms for controlling conductivity may be contained in the surface layer 104 in a state of being uniformly distributed.
Alternatively, there may be a portion containing a non-uniform distribution in the layer thickness direction.

The thickness of the surface layer 104 in the present invention is usually 20Å to 10 μm, preferably 100Å to 5 μm.
m, most preferably 500Å to 2 μm. That is, if the thickness is less than 20Å, the effect of the present invention cannot be sufficiently obtained, and the surface layer may be lost due to abrasion during use of the light receiving member. Further, when the layer thickness exceeds 10 μm, deterioration of electrophotographic characteristics such as increase of residual potential is observed.

The surface layer 104 according to the present invention is carefully formed to provide its desired properties as desired. That is, Si, C and / or N and / or O,
A substance having H as a constituent structurally takes a form from crystalline to amorphous depending on its forming condition, and has an electrical property ranging from conductive to semiconducting to insulating.
Further, since each of the properties from the photoconductive property to the non-photoconductive property is shown, in the present invention, the formation conditions of the compound having desired properties depending on the purpose are formed according to the desired conditions. The choice is made strictly. For example, in order to provide the surface layer 104 mainly for improving the pressure resistance,
It is made as a non-single-crystal material that has an electrically insulating behavior in the environment of use. Further, when the surface layer 104 is provided mainly for the purpose of improving continuous repeated use characteristics and use environment characteristics, the non-single crystal having a high degree of hardness or a high water repellency is relaxed to some extent in the degree of the electric insulation. Formed as a material.

In the present invention, it is also possible to provide another blocking layer (lower surface layer) composed of SiC (H, X) having a reduced content of nitrogen atoms between the photoconductive layer and the surface layer. It is effective for further improving characteristics such as Noh. Further, the surface layer 104 and the photoconductive layer 103 of the present invention
A region in which the content of carbon atoms and / or nitrogen atoms changes so as to decrease toward the photoconductive layer 103 may be provided between and. This can further reduce the influence of interference due to the reflected light at the interface between the surface layer and the photoconductive layer.

[0064]

[Manufacturing Method] An apparatus and a forming method for forming a deposited film by a high frequency plasma CVD method and a microwave plasma CVD method will be described in detail below. FIG. 6 is a schematic explanatory view showing an example of a manufacturing apparatus of a photoreceptive member for electrophotography by a high frequency plasma CVD (hereinafter referred to as “RF-PCVD”) method, and FIG. 7 is a microwave plasma CVD.
FIG. 3 is a schematic explanatory view showing an example of a deposited film forming reaction furnace for forming a deposited film for an electrophotographic light receiving member by a method (hereinafter referred to as “μW-PCVD”).

The deposited film is formed by using the deposited film manufacturing apparatus by the RF-PCVD method shown in FIG. 6, for example, as follows. This apparatus is roughly divided into a deposition apparatus 6100, a source gas supply apparatus 6200, and an exhaust apparatus (not shown) for reducing the pressure inside the reaction vessel 6111. First, the cylindrical support 6112 is installed in the reaction container 6111, and the inside of the reaction container 6111 is exhausted by an exhaust device (not shown) (for example, a vacuum pump). Then, the temperature of the cylindrical support 6112 is set to 20 by the heater 6113 for heating the support.
The temperature is controlled to a predetermined temperature of ℃ to 500 ℃.

A raw material gas for forming a deposited film is supplied to the reaction vessel 611.
In order to make it flow into 1, the gas cylinder valves 6231-6
236, make sure that the leak valve 6117 of the reaction vessel is closed, and check the inflow valves 6241 to 624.
6, outflow valves 6251 to 6256, auxiliary valve 626
Make sure 0 is open, then first open the main valve 6
118 is opened and the reaction vessel 6111 and the gas pipe 61 are opened.
Evacuate 16. Next, the reading of the vacuum gauge 6119 is about 5 × 1
When the pressure reaches 0 ^-6 Torr, the auxiliary valve 6260 and the outflow valves 6251 to 6256 are closed. After that, the gas cylinders 6221 to 6226 supply the gases to the valves 6231 to 632.
236 is opened and introduced, and pressure regulators 6261-6266
Each gas pressure is adjusted to ² Kg / cm ² by. Next, the inflow valves 6241 to 6246 are gradually opened to introduce each gas into the mass flow controllers 6211 to 6216.

After the preparation for film formation is completed as described above, the photoconductive layer and the surface layer are formed on the cylindrical support 6112. First, when the cylindrical support 6112 reaches a predetermined temperature, the necessary ones of the outflow valves 6251 to 6256 and the auxiliary valve 6260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 6221 to 6226 via the gas introduction pipe 6114. It is introduced into the reaction container 6111. Next, mass flow controllers 6211-6216
Is adjusted so that each source gas has a predetermined flow rate. At that time, the opening of the main valve 6118 is adjusted while observing the vacuum gauge 6119 so that the pressure in the reaction vessel 6111 becomes a predetermined pressure of 1 Torr or less. When the internal pressure is stable, the RF power source (not shown) is set to a desired power, and the RF power is introduced into the reaction vessel 6111 through the high frequency matching box 6115 to cause the RF glow discharge. The raw material gas introduced into the reaction vessel is decomposed by this discharge energy, and the cylindrical support 6112
This is where a predetermined deposited film containing silicon as a main component is formed. After the desired film thickness is formed, the supply of 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. Then, by repeating the same operation a plurality of times, a light receiving layer having a desired multilayer structure is formed.

Needless to say, all the outflow valves other than the necessary gas are closed when forming the respective layers, and the respective gases are used for the reaction vessel 6111.
Inside, outflow valves 6251 to 6256 to reaction vessel 611
In order to avoid unnecessary gas remaining in the pipe reaching 1, the outflow valves 6251 to 6256 are closed, the auxiliary valve 6260 is opened, and the main valve 6118 is fully opened to once exhaust the system to a high vacuum. Perform operations as needed.

In order to make the film formation uniform, the cylindrical support 6112 is rotated at a predetermined speed by a driving device (not shown) during the film formation. Needless to say, the above-mentioned gas species and valve operation may be changed according to the preparation conditions of each layer.

Next, a method for manufacturing the electrophotographic light-receiving member formed by the μW-PCVD method will be described.
By replacing the deposition apparatus 6100 by the RF-PCVD method in the manufacturing apparatus shown in FIG. 6 with the deposition apparatus 7100 shown in FIG. 7 and connecting it to the source gas supply apparatus 6200, μ
It is possible to obtain an electrophotographic light-receiving member manufacturing apparatus by the W-PCVD method.

The deposited film is formed using this apparatus, for example, as follows. First, a cylindrical support 7115 is installed in the reaction container 7111, the support 7115 is rotated by a driving device 7120, and the reaction container 7111 is exhausted through an exhaust pipe 7121 by an exhaust device (not shown) (for example, a vacuum pump). Then, the pressure in the reaction vessel 7111 is set to 1 × 10 ⁻⁶ To.
Adjust to rr or less. Then, the heater 7 for heating the support
116, the temperature of the cylindrical support 7115 is set to 20 ° C. to 5 ° C.
It is heated and maintained at a predetermined temperature of 00 ° C.

A source gas for forming a deposited film is supplied to a reaction vessel 711.
In order to make it flow into 1, the gas cylinder valves 6231-6
236, make sure that the leak valve (not shown) of the reaction vessel is closed, and check the inflow valves 6241-6
246, outflow valves 6251 to 6256, auxiliary valve 6
After confirming that 260 is open, first, a main valve (not shown) is opened to evacuate the inside of the reaction vessel 7111 and the gas pipe 7122. Next, when the reading of the vacuum gauge (not shown) reaches about 5 × 10 ⁻⁶ Torr, the auxiliary valve 6
260, the outflow valves 6251-6256 are closed. After that, each gas is introduced from the gas cylinders 6221 to 6226 by opening the valves 6231 to 6236, and the pressure regulator 626.
Each gas pressure is adjusted to ² Kg / cm ² by 1-6266. Next, the inflow valves 6241 to 6246 are gradually opened to allow the respective gases to flow through the mass flow controllers 6211 to 62.
Installed in 16.

After the preparation for film formation is completed as described above, the photoconductive layer and the surface layer are formed on the cylindrical support 7115. First, when the cylindrical support 7115 reaches a predetermined temperature, the necessary ones of the outflow valves 6251 to 6256 and the auxiliary valve 6260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 6221 to 6226 via the gas introduction pipe 7117. And is introduced into the discharge space 7130 in the reaction vessel 7111. Next, the mass flow controllers 6211 to 6216 are adjusted so that each raw material gas has a predetermined flow rate. At that time, the opening of the main valve (not shown) is adjusted while observing the vacuum gauge (not shown) so that the pressure in the discharge space 7130 becomes a predetermined pressure of 1 Torr or less. After the pressure has stabilized, a microwave power source (not shown) generates microwaves having a frequency of 500 MHz or more, preferably 2.45 GHz, and the microwave power source (not shown) is set to a desired power to guide the waves. Tube 711
3, discharge space 713 through microwave introduction window 7112
The μW energy is introduced to 0 to generate the μW glow discharge. Simultaneously with this, the power source 7119 to the electrode 7
An electrical bias such as direct current is applied to 118. Thus, the discharge space 71 surrounded by the support body 7115.
In 30, the introduced source gas is excited by the energy of microwaves to dissociate, and the cylindrical support 711
A predetermined deposited film is formed on the film 5. At this time, in order to make the layer formation uniform, the support rotating motor 7120 is rotated at a desired rotation speed.

After the desired film thickness is formed, the supply of μW electric power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed. By repeating the same operation a plurality of times, a desired light-receiving layer having a multilayer structure is formed.

Needless to say, all the outflow valves other than the necessary gas are closed when forming each layer, and each gas is supplied to the reaction vessel 7111.
Inside, outflow valves 6251 to 6256 to reaction vessel 711
In order to avoid remaining in the pipe up to 1, the outflow valves 6251 to 6256 are closed, the auxiliary valve 6260 is opened, and the main valve (not shown) is fully opened to temporarily exhaust the system to a high vacuum. Do as needed. Needless to say, the above-mentioned gas species and valve operation may be changed according to the preparation conditions of each layer.

The method of forming the metal atoms in the light-receiving layer formed as described above so as to have a two-dimensional distribution is not limited to the RF-PCVD method and the μW-PCVD method. The method is the same as that described for the metal atom.

The contents of the experiment leading to the present invention will be described below.

[0078]

[Experiment 1] A photosensitive drum for electrophotography was formed as follows using a deposited film forming apparatus by a high-frequency plasma CVD (hereinafter referred to as "RF-PCVD") method shown in FIG. For film formation, first, an aluminum cylinder (cylindrical support) 61 having a mirror finish in a reaction vessel 6111.
12, the cylindrical support 6112 is rotated at a predetermined speed by a driving device (not shown) in order to make the film formation uniform if necessary. Next, the inside of the reaction vessel 6111 was exhausted by an exhaust device (not shown) (for example, a vacuum pump). Then, the temperature of the cylindrical support 6112 was controlled to a predetermined temperature of 20 ° C. to 500 ° C. by the heater 6113 for heating the support.

A raw material gas for forming a deposited film is supplied to the reaction vessel 611.
Gas cylinder valve 6231-
6236, make sure that the leak valve 6117 of the reaction vessel is closed, and check the inflow valves 6241-62.
46, outflow valves 6251 to 6256, auxiliary valve 62
After confirming that 60 is open, first open the main valve 6118 to open the reaction vessel 6111 and the gas pipe 61.
The inside of 16 was evacuated. Next, the reading of the vacuum gauge 6119 is about 5 ×
When the pressure reached 10 ⁻⁶ Torr, the auxiliary valve 6260 and the outflow valves 6251 to 6256 were closed. After that, each gas is introduced from the gas cylinders 6221 to 6226 required for film formation by opening the valves 6231 to 6236, and the pressure regulator 62 is introduced.
Each gas pressure was adjusted to ² Kg / cm <2> by 61-6266. Next, the inflow valves 6241 to 6246 are gradually opened to allow the respective gases to flow through the mass flow controllers 6211 to 621.
216. After the preparation for film formation was completed as described above, a photoconductive layer was formed on the cylindrical support 6112 under the manufacturing conditions shown in Table 1.

When the cylindrical support 6112 reaches a predetermined temperature, the necessary ones of the outflow valves 6251 to 6256 and the auxiliary valve 6260 are gradually opened to supply a predetermined gas from the gas cylinders 6221 to 6226 to the gas introduction pipe 6.
It is introduced into the reaction vessel 6111 via 114. Next, the mass flow controllers 6211 to 6216 were adjusted so that each raw material gas had a predetermined flow rate. that time,
The opening of the main valve 6118 was adjusted while observing the vacuum gauge 6119 so that the pressure inside the reaction vessel 6111 became 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 container 6111 is passed through a high frequency matching box 6115.
RF power was introduced into the chamber to cause RF glow discharge.
The source energy introduced into the reaction vessel is decomposed by this discharge energy, and a predetermined deposited film containing silicon as a main component is formed on the cylindrical support 6112. After the desired film thickness was formed, the supply of RF power was stopped, the outflow valve was closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film was completed.

By repeating the same operation a plurality of times, a light receiving layer having a desired multilayer structure was formed. When forming each layer, all the outflow valves other than the necessary gas are closed, and each gas is stored in the reaction vessel 6111.
In order to avoid remaining in the pipe from the outflow valves 6251 to 6256 to the reaction vessel 6111, the outflow valves 6251 to 6256 are closed, the auxiliary valve 6260 is opened, and the main valve 6118 is fully opened to once bring the system into a high vacuum state. The operation to evacuate was performed.

In the light-receiving layer formed as described above, a metal film of zinc (Zn) is formed on the surface by a metal deposition apparatus shown in FIG. 8 so that regions containing metal atoms have a two-dimensional distribution. Formed. First, the vacuum vessel 801 was evacuated through the exhaust pipe 808 by a vacuum pump (not shown), and the pressure in the vacuum vessel 801 was adjusted to 1 × 10 ⁻⁷ Torr or less.
Then, the Zn-containing crucible 802 was heated to generate a metal vapor flow 804. During formation of the metal thin film, the cylindrical support 8 is heated to a predetermined temperature by the heater 806 so that Zn atoms easily move to the dangling bond on the surface of the light receiving layer.
05 was kept heated. At the same time, the rotating shaft 807 was rotated to deposit a metal thin film on the entire surface of the support 805. At this time, not only the substrate temperature described above, but also the pressure, vapor deposition rate, vapor deposition time, etc. were optimally controlled so that the vapor deposited metal film had a two-dimensional distribution.

In this experiment, the heating temperature of the drum and the deposition amount were changed in order to change the coating area while maintaining the size of each island to be approximately 3000 Å in diameter. Although the tendency greatly differs depending on the type of metal, when the drum temperature is raised roughly, the diameter of the island becomes smaller, and conversely, when the deposition amount increases, the island size and the coverage rate tend to increase. The optimum conditions were selected.

In this experiment, the size of the metal island and the coverage are X.
Although it was determined by the surface analysis by the line micro analysis, the same information can be obtained by the surface analysis by the Auger electron spectroscopic analysis or the surface analysis by SIMS when the amount of adhered metal atoms is small.

The electrophotographic light-receiving member with the metal coverage changed in this way was set in an electrophotographic apparatus (NP6060 manufactured by Canon Inc. modified for this test) and subjected to various conditions. In addition, the image defects were evaluated as follows based on the image defect enlargement ratio and the white spot level in addition to the electrophotographic characteristics such as the initial chargeability, residual potential, and image deletion.

Charging ability: The photoreceptive member for electrophotography was installed in the experimental apparatus, a high voltage of +6 kV was applied to the charger to perform corona charging, and the surface potential of the photoreceptive member for electrophotography in the dark area was measured. To do.

Residual potential: The electrophotographic light-receiving member is charged to a constant dark surface potential. Immediately, a relatively strong light of a constant light quantity is applied. The light image was emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the light portion of the electrophotographic light-receiving member is measured with a surface potential meter.

The evaluation categories for each are as follows. A: Very good B: Good B: Conventional level, no problem in practical use X: Lighter density or fogging occurs, causing a problem in practical use

Image deletion ... Under a high humidity environment (temperature: 40 ° C., humidity: 80%), a Canon test chart (part number: FY9-9058) consisting of all letters on a white background is placed on a document table and the normal exposure amount is applied. Irradiate with and make a copy. The obtained copy image was observed, and it was evaluated whether the fine line on the image was blurred. However, at this time, when there was unevenness on the image, the evaluation was performed on the entire image area and the result of the worst part was shown. The evaluation categories are as follows. ⊚: Very good with no blur observed ○: Good with slightly blunted edges of the character △: Can be recognized as a character with some blur, but is not a problem in practice ×: Unrecognizable character There is a problem in practical use

Image defect magnifying power: The toner image on the light receiving member before transfer is observed with a microscope, and the area of the area around the spherical protrusions where the toner is not adhered is measured. Next, the toner image is removed, and the area of the spherical protrusion in the same portion is measured. After that, (area of toner-free area /
The area of the spherical protrusions) is calculated. The evaluation categories are as follows. ⊚: the ratio is substantially 2 or less ∘: the ratio exceeds 2, and 10 or less Δ ... exceeds 10 and 100 or less × ... exceeds 100

White Pochi ... A diameter 0.2 within the same area of a copy image obtained when a Canon full-face black chart (part number: FY9-9073) is placed on a platen and copied.
White spots having a size of mm or more were evaluated. The evaluation categories are as follows. ◎… Very good ○… Good △… There are white spots, but there is no problem in practical use at the conventional level ×… There are many white spots and there are problems in practical use

Table 2 shows the evaluation results. From this experiment, it was confirmed that the characteristics of the electrophotographic photosensitive drum were remarkably improved by making the region where the metal atoms exist in the range of 5% to 60% of the surface.

[0093]

[Experiment 2] An electrophotographic light-receiving member was formed under the production conditions shown in Table 1 using the same production apparatus and production method as in Experiment 1. However, in this experiment, the metal element was chromium (Cr), and the distribution shape of the islands of the metal thin film was changed by appropriately changing the heating temperature of the photosensitive drum, the vapor deposition speed, and the vapor deposition amount.

The sample 1 had a substantially circular island shape shown in FIG. Sample 2, as shown in FIG. 2, had a slightly deformed island shape. As shown in FIG. 3, the sample 3 had a shape in which the metal coating did not adhere in a substantially circular pond shape. As shown in FIG. 4, Sample 4 had a shape in which the metal film was not slightly deformed and attached in a pond shape.

The coverage of each sample was almost 50%.
And the electrophotographic characteristics such as charging ability, residual potential, and image characteristics were evaluated in the same manner as in Experiment 1. The results are shown in Table 3. From this result, it was found that the light receiving member, in the initial state, has a remarkable effect even if it is attached to any shape.

[0096]

[Experiment 3] Using the electrophotographic light-receiving member prepared in Experiment 2 in a high-humidity environment at a temperature of 40 ° C. and a humidity of 85%, using recycled paper 1
After the endurance test of copying 0,000 sheets, the same evaluation as the initial stage was performed. Table 4 shows the evaluation results. From the results shown in Table 4, it was found that the island-shaped attachment shape of the metal atoms on the surface of the light receiving member is more effective.

[0097]

[Experiment 4] Using the same production apparatus and production method as in Experiment 1, an electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder (support). At this time, the manufacturing conditions of the photoconductive layer were as shown in Table 1. However, the metal atom was nickel (Ni), and this time, the diameter of the island was changed while controlling the deposition conditions such as the heating temperature of the photosensitive drum and the deposition amount to maintain the coverage rate at about 30%. .
The electrophotographic light-receiving member thus produced was evaluated for electrophotographic characteristics such as charging ability, residual potential and image characteristics in the same manner as in Experiment 1. The results are shown in Table 5. From this result, it was found that the most effective diameter of the island is 200Å to 5000Å.

[0098]

[Experiment 5] An electrophotographic light-receiving member was formed under the conditions shown in Table 1 using the same production apparatus and production method as in Experiment 1. However, this time, a metal thin film having a two-dimensional structure was selectively formed by using various metal atoms. In each of the samples, the shape of the region in which the metal element exists was a shape approximate to a circle or an ellipse, and the size was adjusted so that the diameter (major axis) was 5000Å and the coverage was about 40%. These light receiving members were subjected to the same evaluation as in Experiment 1. The results are shown in Table 6. From this result, the types of metal atoms present on the surface were determined to be Ib, IIb,
IIIa, IVa, Va, VIa, VIIa, VIII
It was revealed that the electrophotographic light-receiving member, which is at least one element selected from the group, has a more remarkable effect.

[0099]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[0100]

Example 1 An electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder (support) using the manufacturing apparatus by the RF-PCVD method shown in FIG. At this time, the manufacturing conditions of the photoconductive layer were as shown in Table 7. By controlling the deposition conditions such as the temperature of the support and the deposition amount and the deposition time on the surface of the light receiving member thus produced by the deposition apparatus shown in FIG. 8, the size is about 50 mm in diameter.
A metal thin film was selectively formed in an island shape so that the coating ratio was 00Å and the coverage was about 20%. Copper (Cu) was used as the metal.

The electrophotographic light-receiving member thus manufactured was set in an electrophotographic apparatus (NP6060 manufactured by Canon Inc. was modified for this test), and the initial charging ability was set under various conditions. In addition to the electrophotographic characteristics such as residual potential and image deletion, the image defect enlargement ratio and white spot were measured as follows.

Charging ability: A photoreceptive member for electrophotography is installed in an experimental apparatus, a high voltage of +6 kV is applied to a charger to carry out corona charging, and the surface potential of the photoreceptive member for electrophotography in a dark area is measured. To do.

Residual potential: The photoreceptive member for electrophotography is charged to a constant dark surface potential. Immediately, a relatively strong light of a constant light quantity is applied. The light image was emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the light receiving member for electrophotography is measured with a surface potential meter

The evaluation categories for each are as follows. A: Very good B: Good B: No particular advantage, but practically no problem X: Practical problem due to low density or fogging

Image deletion: In a high humidity environment (temperature: 40 ° C, humidity: 80%), a Canon test chart (part number: FY9-9058) consisting of all letters on a white background is placed on a document table and the normal exposure amount is applied. Irradiate with and make a copy. The obtained copy image was observed, and it was evaluated whether the fine line on the image was blurred. However, at this time, when there was unevenness on the image, the evaluation was performed on the entire image area and the result of the worst part was shown. The evaluation categories are as follows. ⊚: Very good with no blurring observed ○: Good with slightly blunted edges of the character △: Some blurring but recognizable as a character, practically no problem ×: Unrecognizable character There is a problem in practical use

Image defect magnifying power: The toner image before transfer on the light receiving member is observed with a microscope, and the area of the area around the spherical protrusions where the toner is not attached is measured. Next, the toner image is removed, and the area of the spherical protrusion in the same portion is measured. After that, (area of toner-free area /
The area of the spherical protrusions) is calculated. The evaluation categories are as follows. ⊚: the ratio is substantially 2 or less ∘: the ratio exceeds 2, and 10 or less Δ ... exceeds 10 and 100 or less × ... exceeds 100

White Pochi ... A diameter 0.2 within the same area of the copy image obtained when the Canon full-face black chart (part number: FY9-9073) is placed on the platen and copied.
White spots having a size of mm or more were evaluated. The evaluation categories are as follows. A: Very good O: Good B: White spots are present, but there is no problem in practical use at the conventional level. X ... Many white spots are present, and there are problems in practical use. Table 8 shows the evaluation results.

[0108]

Comparative Example 1 Using the manufacturing apparatus shown in FIG. 6, after forming the light receiving member under the manufacturing conditions shown in Table 7 in the same manner as in Example 1, the operation was carried out without attaching metal atoms (coverage 0%). The same evaluation as in Example 1 was performed. The results are also shown in Table 8. From the results of Example 1 and Comparative Example 1, it was confirmed that the light receiving member according to the present invention was significantly superior to the light receiving members outside the scope of the present invention. Furthermore, when the distribution state of copper (Cu) of the light receiving member of the present invention on the surface of the light receiving member was analyzed by two-dimensional mapping by X-ray microanalysis, Cu was found to be a feature of the present invention. The two-dimensional distribution was observed on the surface.

[0109]

Comparative Example 2 The surface of the light receiving member was prepared by polishing the light receiving member produced in Comparative Example 1 according to the method disclosed in JP-A-61-231558 using Cu as a polishing agent. At least a part of the reaction product produced by the solid-phase reaction of the treating agent was mechanically removed. After this treatment, the same evaluation as in Example 1 was performed. The results are also shown in Table 8. Even if the surface treatment was performed, the charging ability and the dark decay were not improved as much as the present invention. Furthermore, when the distribution state of Cu on the surface of the light receiving member was analyzed by two-dimensional mapping by X-ray microanalysis, Cu was uniformly distributed on the surface of the light receiving member, and it was found that the columnar structure had columns as in the present invention. No localization was observed between the pillars.

[0110]

Example 2 An electrophotographic light-receiving member was formed on a mirror-finished aluminum cylinder (support) using the manufacturing apparatus by the RF-PCVD method shown in FIG. At this time, the manufacturing conditions of the photoconductive layer were as shown in Table 9. On the surface of the light receiving member thus produced, the size is about 3 mm in diameter by controlling the deposition temperature and the deposition conditions such as the support temperature and the deposition time by the deposition apparatus shown in FIG.
A metal thin film was selectively formed in an island shape so that the coating rate was 000Å and the coverage was about 25%. Titanium (Ti) was used as the metal. The electrophotographic light-receiving member thus produced was evaluated in the same manner as in Example 1. The results are shown in Table 10. As a result, a light receiving member having a good contrast with few image defects was obtained.

[0111]

Comparative Example 3 A light-receiving member was formed according to the manufacturing conditions shown in Table 11 using the same apparatus and procedure as in Example 2. In this comparative example, similarly to the technique disclosed in JP-A-60-28658, Ti metal pulverized to the micron order is introduced as a carrier gas at the end of film formation to introduce Ti metal into the film. did. The electrophotographic light-receiving member thus produced was evaluated in the same manner as in Example 1 and the results are also shown in Table 10. The chargeability and dark decay were not improved. Furthermore, when the distribution state of Ti on the surface of the light receiving member was analyzed by two-dimensional mapping by X-ray microanalysis, Ti was uniformly distributed on the surface of the light receiving member, and it was localized in the two-dimensional state as in the present invention. I couldn't see him there.

[0112]

Comparative Example 4 A light-receiving member was formed according to the manufacturing conditions shown in Table 12 using the same apparatus and procedure as in Example 2. In this comparative example, B atoms were introduced into the film by introducing 100 ppm of B ₂ H ₆ just before the completion of film formation. The electrophotographic light-receiving member thus produced was evaluated in the same manner as in Example 1. The results are also shown in Table 10. The chargeability and dark decay were not improved. Further, when the distribution state of B on the surface of the light receiving member was analyzed by two-dimensional mapping by X-ray microanalysis, B was uniformly distributed on the surface of the light receiving member, and thus, B having a columnar structure as in the present invention was obtained. No localization was observed between the pillars.

[0113]

[Comparative Example 5] A light-receiving member was formed according to the manufacturing conditions shown in Table 13 by the same apparatus and procedure as in Example 2. In this comparative example, P atoms were introduced into the film by introducing 100 ppm of PH ₃ just before the completion of film formation. The electrophotographic light-receiving member thus produced was evaluated in the same manner as in Example 1. The results are also shown in Table 10. The chargeability and dark decay were not improved. Furthermore, when the distribution state of P on the surface of the light receiving member was analyzed by two-dimensional mapping by X-ray microanalysis, P was uniformly distributed on the surface of the light receiving member, and it was confirmed that the pillars having the columnar structure as in the present invention were formed. No localization was observed between the pillars.

[0114]

Example 3 An electrophotographic light-receiving member was formed under the manufacturing conditions shown in Table 14 by using the same manufacturing apparatus and manufacturing method as in Example 1. However, this time, a plurality of transition metal atoms were used in combination to selectively form a metal thin film having a two-dimensional structure. The metal was previously melted to prepare an alloy, and then a thin film was deposited by the vapor deposition device shown in FIG. In both samples, the shape of the region in which the metal element exists is a circle, or a shape close to an ellipse,
A metal thin film was selectively formed in an island shape with a diameter (major axis) of 4000Å and a coverage of about 50%. The electrophotographic light-receiving member thus produced was evaluated in the same manner as in Example 1. The results are shown in Table 15. Image defects were good. From these results, it was confirmed that the light receiving member according to the present invention has the same effect even if the metal atoms present on the surface are plural elements.

[0115]

Example 4 An electrophotographic light-receiving member was formed in the same manner as in Example 1 using the manufacturing apparatus by the RF-PCVD method shown in FIG. At this time, the production conditions of the photoconductive layer were as shown in Table 16, and a surface protective layer made of SiC was further provided on the photoconductive layer. An island-shaped metal thin film was selectively formed on the surface of the light-receiving member thus produced by an electron beam evaporation apparatus. Iron (Fe) is used as the metal, and the shape of the region where the metal element exists is a shape close to a circle or an ellipse. The size is a diameter (major axis) of about 2500Å and the coverage is 60.
%. The electrophotographic light-receiving member thus produced was evaluated for electrophotographic characteristics such as charging ability, residual potential, image deletion, image defect enlargement ratio and white spots in the same manner as in Example 1. Table 17 shows the evaluation results. It was found that the same effect can be obtained when the present invention is applied to a light receiving member having a surface layer.

[0116]

Example 5 The electrophotographic light-receiving member produced in Example 4 was set in an electrophotographic apparatus (NP6060 manufactured by Canon Inc.), and recycled paper was used under a high humidity environment of a temperature of 40 ° C. and a humidity of 85%. After the durability test of copying 100,000 sheets, the same evaluation as the initial stage was performed. The results are shown in Table 17, and the same results as in Example 4 were obtained.

[0117]

Example 6 A photoconductive layer and a surface layer made of SiC were formed under the manufacturing conditions shown in Table 18 using the deposited film forming apparatus by the μW-PCVD method shown in FIG. A metal thin film was selectively formed in an island shape on the surface of the light-receiving member thus produced by controlling the vapor deposition conditions, vapor deposition time and the like with an ion beam vapor deposition apparatus. The size of the island is about 1500
Å, the coverage was 10%, and zinc (Zn) was used as the metal. When this electrophotographic light-receiving member was subjected to the same evaluations as in Example 1, the same favorable results as in Table 17 were obtained. From this, it is recognized that the electrophotographic light-receiving member within the scope of the present invention is significantly superior to the electrophotographic light-receiving member outside the scope of the present invention, regardless of the method for producing the light-receiving layer and the surface layer. I was able to confirm that.

[0118]

Example 7 The electrophotographic light-receiving member produced in Example 6 was set in an electrophotographic apparatus (NP6060 manufactured by Canon Inc.), and recycled paper was placed in a high humidity environment at a temperature of 40 ° C. and a humidity of 85%. After an endurance test in which 100,000 copies were used, the same evaluation as in the initial stage was performed, and the same results as in Table 17 were obtained.

[0119]

[Embodiment 8] Using the deposition film forming apparatus by the μW-PCVD method shown in FIG. 7, a function-separated type light receiving member consisting of a charge transport layer, a charge generation layer, and a surface layer is formed under the manufacturing conditions shown in Table 19. did. A metal thin film was selectively formed in an island shape on the surface of the light-receiving member thus produced by controlling the vapor deposition conditions, vapor deposition time and the like with an ion beam vapor deposition apparatus. The size of the island was about 2000Å, the coverage was 30%, and cobalt (Co) was used as the metal. When this drum was evaluated in the same manner as in Example 1, the same good results as in Table 17 were obtained. From these facts, it was confirmed that the electrophotographic light-receiving member of the present invention has remarkably excellent characteristics regardless of the layer structure of the light-receiving member.

[0120]

[Table 1]

[0121]

[Table 2]

[0122]

[Table 3] (Evaluation before endurance)

[0123]

[Table 4] (Evaluation after endurance)

[0124]

[Table 5]

[0125]

[Table 6]

[0126]

[Table 7]

[0127]

[Table 8]

[0128]

[Table 9]

[0129]

[Table 10]

[0130]

[Table 11]

[0131]

[Table 12]

[0132]

[Table 13]

[0133]

[Table 14]

[0134]

[Table 15]

[0135]

[Table 16]

[0136]

[Table 17]

[0137]

[Table 18]

[0138]

[Table 19]

[0139]

According to the present invention, it is possible to easily provide an electrophotographic light-receiving member having very few image defects, which has hitherto been difficult to achieve even in an extremely clean environment. It was In the electrophotographic light-receiving member according to the present invention, the above-mentioned effects can be obtained without side effects such as image deletion and sensitivity deterioration by allowing a transition metal to be present on the outermost surface in a two-dimensional distribution. The feature is that the effect is maintained.

[Brief description of drawings]

FIG. 1 is a schematic layer configuration diagram for explaining a layer configuration of a light receiving member for electrophotography of the present invention.

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

FIG. 3 is a schematic layer structure diagram for explaining the layer structure of the electrophotographic light-receiving member of the present invention.

FIG. 4 is a schematic layer structure diagram for explaining the layer structure of the electrophotographic light-receiving member of the present invention.

FIG. 5 is a schematic layer structure diagram for explaining the layer structure of the electrophotographic light-receiving member of the present invention.

FIG. 6 is a schematic explanatory view showing an example of an apparatus for manufacturing an electrophotographic photosensitive drum by high-frequency discharge for forming a light receiving layer of an electrophotographic light receiving member of the present invention.

FIG. 7 is a schematic explanatory view showing an example of an apparatus for manufacturing an electrophotographic photosensitive drum by microwave discharge for forming a light receiving layer of the electrophotographic light receiving member of the present invention.

FIG. 8 is a schematic explanatory view showing an example of an evaporation apparatus for evaporating metal atoms of the electrophotographic light-receiving member of the present invention.

[Explanation of symbols]

 100 Photoreceptive member 101 Support 102 Photoreceptive layer 103 Photoconductive layer 104 Surface layer 105 Metal atom existing on the surface 106 Free surface

Claims (7)

[Claims] 1. A photoreceptive member for electrophotography, wherein at least the outermost surface portion is made of a non-single crystalline material containing silicon atoms. A light for electrophotography, wherein one kind of metal atom exists, and a region where the metal atom exists and a region where the metal atom does not substantially exist are two-dimensionally distributed on the outermost surface. Receiving member. 2. The electrophotographic light-receiving member is composed of a support and a non-single-crystal material having a silicon atom as a base material arranged on the support, and the non-single-crystal material exhibits photoconductivity. The light-receiving member for electrophotography according to claim 1, characterized in that. 3. The light receiving member for electrophotography according to claim 1, further comprising a surface protective layer on the non-single crystal material. 4. The light receiving member for electrophotography according to claim 1, wherein the coverage of the metal covering the surface of the light receiving member for electrophotography is 5% or more and 60% or less. . 5. The outermost surface of the electrophotographic light-receiving member contains the region where the metal atom is present, distributed in an island shape in the region where the metal atom is substantially absent. The light-receiving member for electrophotography according to claim 1, wherein the light-receiving member is for electrophotography. 6. The region where the metal atoms are present in an island shape,
The electrophotographic light-receiving member according to claim 5, wherein the light-receiving member for electrophotography is approximate to a circle and the circular region has a diameter of 200 Å or more and 5000 Å or less. 7. The size of the region where the metal atoms are present in an island shape is approximate to an ellipse, and the elliptical region has a major axis of 200 Å or more and 5000 Å or less. 5. The electrophotographic light-receiving member according to item 5.