JPS6381471A - Photosensitive body - Google Patents

Abstract

PURPOSE:To provide adequate transferability and excellent photoconductivity to a titled photosensitive body by using a hydrogenated amorphous carbon film contg. oxygen atoms to form an electric charge transfer layer and using a hydrogenated or fluorinated amorphous silicon germanium film contg. either of phosphorus atoms or boron atoms to form an electric charge generating layer. CONSTITUTION:This function sepn. type photosensitive body having the charge generating layer 3 and the charge transfer layer 2 is provided with the hydrogenated amorphous carbon film which is formed by glow discharge and into which the oxygen atoms are incorporated as the charge transfer layer 2 and the hydrogenated or fluorinated amorphous silicon germanium film which is likewise formed by the glow discharge and into which at least either of the phosphorus atoms or boron atoms are incorporated as the charge generating layer 3. High dark resistance and excellent electric charge transferability are thereby provided to the charge transfer layer 2 so that said layer can make contribution to bright attenuation. The carriers generated in the formed film are efficiently implanted into the charge generating layer 3 in the lamination constitution with the charge transfer layer 2 so that said layer can make adequate contribution to the bright attenuation.

Description

[Detailed description of the invention] Cliff! FIELD OF THE INVENTION The present invention relates to a photoreceptor having a charge generation layer and a charge transport layer.

BACKGROUND OF THE INVENTION Since the invention of the Carlson method, the application field of electrophotography has continued to make remarkable progress, and various materials have been developed and put into practical use for electrophotographic photoreceptors.

The main electrophotographic photoreceptor materials conventionally used include inorganic substances such as amorphous selenium, selenium arsenide, selenium telluride, cadmium sulfide, zinc oxide, amorphous silicon, polyvinyl carbazole, metal phthalocyanine,
Examples include organic substances such as disazo pigments, trisazo pigments, perylene pigments, triphenylmethane compounds, triphenylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, oxazole compounds, and oxadiazole compounds. In addition, the configurations include a single-layer structure in which these substances are used alone, a binder-type structure in which they are dispersed in a binder, and a laminated structure in which a charge generation layer and a charge transport layer are provided for each function. Can be mentioned.

However, the electrophotographic photoreceptor materials conventionally used each have drawbacks. One of these is their toxicity to the human body, and all inorganic substances, except for the amorphous silicon mentioned above, have unfavorable properties. In addition, in order for an electrophotographic photoreceptor to be actually used in a copying machine, it must always maintain stable performance even when exposed to harsh environmental conditions such as charging, exposure, development, transfer, neutralization, and cleaning. However, all of the organic substances mentioned above have poor durability and many unstable factors in terms of performance.

In order to eliminate such drawbacks, in recent years, amorphous silicon produced by a glow discharge method has been increasingly applied to electrophotographic photoreceptors as a material with improved toxicity and high durability. However, while amorphous silicon requires a large amount of silane gas as a raw material, it is an expensive gas, so the resulting electrophotographic photoreceptor is also significantly more expensive than a conventional photoreceptor. In addition, there are many inconveniences in production, such as the slow film formation rate and the generation of explosive silane undecomposed products in the form of dust as the film formation time increases. Furthermore, if this dust gets mixed into the photosensitive layer during manufacturing, it will have a significant negative effect on image quality. Generally, amorphous silicon has low charging performance due to its high specific charge rate, and in order to charge it to a predetermined surface potential in a copying machine, it is necessary to increase the thickness of the film, making it difficult to use an expensive amorphous silicon film. It must be allowed to accumulate for a long time.

By the way, the amorphous carbon film itself has been known for a long time as a plasma organic polymerized film, for example, diene (M
, 5hen) and Bell (A, T.

Journal of Applied Polymer Science (Journa Be1l), published in 1973.
l of Applied P.

lymer 5science), Volume 17, pages 885 to 892, the same author also reported in the 1979 American Chemical Society that all organic compounds can be prepared from gases.
can Chemical Society) published by Plasma P
Even in the field of polymerization, its film formability has been discussed.

However, plasma organic polymer films prepared by conventional methods are used only for applications that assume insulation properties, that is, they are considered to be insulating films with a specific resistance of about <1016 Ωcm, like ordinary polyethylene films. Or at least it was used with the recognition that it was such a membrane. Due to the same recognition, its actual use in electrophotographic photoreceptors has been limited to protective layers, adhesive layers, blocking layers, or insulating layers, and has only been used as so-called undercoat layers or overcoat layers.

For example, JP-A-59-28161 discloses a photoreceptor in which a plasma-polymerized polymer layer having a network structure is provided on a substrate as a blocking layer and an adhesive layer, and an amorphous silicon layer is provided on the polymer layer. ing. Japanese Patent Application Publication No. 5
No. 9-38753 discloses that 10 to 100 high-resistance plasma polymerized films of 1013 to 1015 Ωcm, which can be generated from a mixed gas of oxygen, nitrogen, and hydrocarbons, are formed on a substrate as a blocking layer and an adhesive layer, and then an amorphous film is formed. A photoreceptor provided with a silicon layer is disclosed. Unexamined Japanese Patent Publication 1987-
Publication No. 136742 discloses a photoreceptor in which a carbon film of approximately 1 to 5 μm is formed on the surface of the substrate as a protective layer to prevent aluminum atoms from diffusing into the amorphous silicon layer provided on the aluminum substrate during light irradiation. is disclosed.

Japanese Unexamined Patent Publication No. 60-63541 discloses a photosensitive material in which a diamond-like carbon film with a thickness of 200 to 2 μm is provided in the middle as an adhesive layer in order to improve the adhesion between an aluminum substrate and an amorphous silicon layer provided thereon. It is said that the film thickness is preferably 2 μm or less in terms of residual charge.

All of these disclosures are inventions in which a so-called undercoat layer is provided between the substrate and the amorphous silicon layer,
There is no disclosure regarding charge transport properties, and a-3i
However, it does not solve the above-mentioned essential problems.

For example, Japanese Patent Application Laid-Open No. 50-20728 discloses that a polymer film of 0.1 to 1 μm formed by glow discharge polymerization is applied as a protective layer on the surface of a polyvinylcarbazole-selenium photoreceptor.
The photoreceptor provided with m is completely exposed. Japanese Patent Publication No. 59-214
Japanese Patent No. 859 discloses a technique for forming a protective layer on the surface of an amorphous silicon photoreceptor by plasma polymerizing an organic hydrocarbon monomer such as styrene or acetylene to form a film of about 5 μm. JP-A No. 60-61761 discloses a photoreceptor provided with a diamond-like carbon thin film of 500 to 2 μm as a surface protective layer, and it is said that the film thickness is preferably 2 μm or less in terms of light transmission. ing.

JP-A-60-249115 discloses that 0.05 to 5μ
A technique is disclosed in which an amorphous carbon or hard carbon film with a thickness of about 5 am is used as a surface protective layer, and it is said that if the film thickness exceeds 5 am, the activity of the photoreceptor is adversely affected.

All of these disclosures are inventions in which a so-called overcoat layer is provided on the surface of a photoreceptor, and there is no disclosure of charge transport properties, and they do not solve the above-mentioned essential problems of a-3i. .

Further, JP-A-51-46130 discloses an electrophotographic photosensitive plate in which a polymer film of 0.001 to 3 μm is formed on the surface of a polyvinyl carbazole electrophotographic photoreceptor by glow discharge polymerization. However, there is no mention of charge transport properties at all, and it does not solve the above-mentioned essential problems of a-si.

On the other hand, regarding the amorphous silicon film, Spear (W
, E, 5pear) and Recomba (P.

Philosophical Magazine (Philosophica I) published in 1976 by
Since it was reported in Vol. 33, pages 935 to 949 of Magaz 1ne) that it is a material that can control polarity, attempts have been made to apply it to various photoelectric devices. Regarding application to photoreceptors, for example, Japanese Patent Application Laid-open No. 5
6-62254, JP 57-119356, JP 57-177147, JP 57-1
No. 19357, Japanese Patent Application Laid-open No. 177149/1983,
JP-A-57-119357, JP-A-57-177
146, JP 57-177148, JP 57-174448, JP 57-17444
Amorphous silicon photoreceptors containing carbon atoms are disclosed in Japanese Patent Publication No. 9, Japanese Patent Application Laid-Open No. 57-174450, etc., but all of them aim to adjust the photoconductivity of amorphous silicon with carbon atoms. Furthermore, amorphous silicon itself requires a thick film.

While B tries to dissolve, as shown above at W point, plasma organic polymer films conventionally used in electrophotographic photoreceptors have been used as so-called undercoat layers or overcoat layers; It is a membrane that does not require a transport function, and is used based on the judgment that the organic polymer membrane is insulating. Therefore, it can only be used as an extremely thin film with a thickness of about 5 μm at most, and carriers either pass through the film by tunneling effect, or if a tunneling effect cannot be expected, there is virtually no interlayer in terms of residual potential generation. It is only used in thin films that can be used without any damage. Furthermore, amorphous silicon films conventionally used in electrophotography are so-called thick films, which have many disadvantages in terms of cost, productivity, and the like.

While considering the application of amorphous carbon films to electrophotographic photoreceptors, the present inventors found that hydrogenated amorphous carbon films, which were originally thought to be insulating, were made to contain oxygen atoms, resulting in phosphorus. It has been found that when laminated with a hydrogenated or fluorinated amorphous silicon germanium film containing at least one of boron atoms and boron atoms, it has charge transport properties and readily begins to exhibit suitable electrophotographic properties. There are many unclear points in the theoretical interpretation, even for the present inventor, so we cannot discuss the details in detail, but the electrons in a relatively unstable energy state captured in the oxygen atom-containing hydrogenated amorphous carbon film, e.g. The band structure formed by π electrons, unpaired electrons, residual free radicals, etc. is the band structure and conduction band formed by a hydrogenated or fluorinated amorphous silicon germanium film containing at least one of phosphorus atoms and boron atoms. Or, because they have similar energy levels in the valence band, carriers generated in a hydrogenated or fluorinated amorphous silicon germanium film containing at least one of phosphorus atoms and boron atoms can easily contain oxygen atoms. It is presumed that this is because the carriers are injected into the hydrogenated amorphous carbon film and can move suitably through the oxygen atom-containing hydrogenated amorphous carbon film due to the action of the electrons in the relatively unstable energy state mentioned above. .

By utilizing this new knowledge, the present invention solves all of the above-mentioned essential problems of amorphous silicon photoreceptors, and also produces an organic plasma polymerized film, which has completely different purposes and characteristics from conventional ones, especially at least A hydrogenated amorphous carbon film containing oxygen atoms is used as a charge transport layer, and a thin film of hydrogenated or fluorinated amorphous silicon germanium containing at least one of phosphorus atoms and boron atoms is used for charge generation. The purpose is to provide a photoreceptor used as a layer.

Specifically, the present invention provides a functionally separated photoreceptor having a charge generation layer and a charge transport layer, in which the charge transport layer is made of a hydrogenated amorphous material containing at least oxygen atoms generated from a plasma polymerization reaction. The present invention relates to a photoreceptor characterized in that it is a carbon film, and the charge generation layer is a hydrogenated or fluorinated amorphous silicon germanium film containing at least one of phosphorus atoms and boron atoms (hereinafter referred to as the present invention). The charge transport layer according to the invention is referred to as an a-C film, and the charge generation layer is referred to as an a-Si film).

The present invention was developed because, in conventional amorphous silicon photoreceptors, amorphous silicon, which has an excellent function as a charge generation layer, is also used as a charge transport layer, which is sufficient as long as it has charge transport ability even if it does not have charge generation ability. This was done to solve these problems.

That is, the present invention provides a hydrogenated amorphous carbon film containing at least oxygen atoms generated by glow discharge as a charge transport layer, and a hydrogenated amorphous carbon film containing at least oxygen atoms generated by glow discharge as a charge generation layer. The present invention relates to a functionally separated photoreceptor characterized by being provided with a hydrogenated or fluorinated amorphous silicon germanium film containing at least one of the above. The charge transport layer does not have clear photoconductivity for visible light or light with a wavelength near semiconductor laser light, but has suitable transport properties,
In addition, it has excellent electrophotographic photoreceptor performance such as charging ability, durability, weather resistance, and environmental pollution resistance, and it also has excellent translucency, so it can be used even when forming a laminated structure as a functionally separated photoreceptor. This provides an extremely high degree of freedom. In addition, the charge generation layer has excellent photoconductivity for visible light or light with a wavelength near semiconductor laser light, and has an extremely thin film thickness compared to conventional amorphous silicon photoreceptors. It is something that can be put to good use.

In the present invention, an organic compound gas, particularly a hydrocarbon gas, is used to form the a-C film.

The phase state of the hydrocarbon does not necessarily have to be a gas phase at room temperature and normal pressure; it can be used in either a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It is.

There are many types of hydrocarbons that can be used, but examples of saturated hydrocarbons include methane, ethane, propane, butane,
Pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane,
tocosan, tricosane, tetracosan, pentacosan,
Normal paraffins such as hexacosane, heptacosane, octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, etc., as well as isobutane, isopentane, neopentane, isohexane, neohexane, 2.3-dimethylbutane, 2-methylhexane, 3- Ethylpentane, 2,2-dimethylpentane, 2
．． 4-dimethylpentane, 3.3-dimethylpentane,
Tributane, 2-methylhebutane, 3-methylhebutane, 2.2-dimethylhexane, 2,2.5-dimethylhexane, 2,2.3-trimethylpentane, 2,2.4
Isoparaffins such as -trimethylpentane, 2,3°3-trimethylpentane, 2.3.4-trimethylpentane, isonanone, etc. are used. Examples of unsaturated hydrocarbons include ethylene, propylene, isobutylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl -Olefins such as 2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-nonene, needlecene, and allene, methylalene, butadiene, pentadiene, hexadiene,
Diolefins such as cyclopentadiene, triolefins such as ocimene, allocimene, myrcene, hexatriene, acetylene, butadiyne, etc.
゜3-pentadiyne, 2,4-hexadiyne, methylacetylene, 1-butyne, 2-butyne, 1-pentyne, 1
-Hexyne, 1-heptyne, 1-octyne, 1-nonine, 1-decyne, etc. are used.

Examples of alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, Cycloparaffins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, and cycloolefins such as limonene, tervirun, phelandrene, sylvestrene, thuene, carene, pinene, bornylene, kamphuen, fuenchen , cycloundecane, tricyclene, bisabolene, zingiberene, curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, campholene, phylloclatene, bodocarprene, mirene, and other terpenes, as well as steroids, are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, pseudocumene, mesitylene, prenitene, isodurene, durene,
Pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, biphenyl, terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

In general, any compound other than hydrocarbons that can be converted into carbon, such as alcohols, ketones, ethers, and esters, can be used.

The amount of hydrogen atoms contained in the a-C film of the present invention is inevitably determined from the manufacturing aspect of using glow discharge, but it is approximately 30 to 60 atomic percent contained in the a-C film based on the total amount of carbon atoms and hydrogen atoms. Ru. Here, the content of carbon atoms and hydrogen atoms in the film is determined by the conventional method of organic elemental analysis, for example, ○N.
This can be determined by using H analysis.

The amount of hydrogen atoms contained in the a-C film in the present invention varies depending on the form of the film forming apparatus and the conditions during film forming, but for example, increasing the substrate temperature, lowering the pressure, using the raw material hydrocarbon gas, etc. Measures such as lowering the dilution rate of hydrogen, increasing the applied power, lowering the frequency of the alternating electric field, increasing the strength of the direct current electric field superimposed on the alternating electric field, or combinations thereof, can reduce the amount of hydrogen contained. It has the effect of lowering

The thickness of the a-C film as the charge transport layer in the present invention is 5 to 5
A suitable value is 0 μm, especially 7 to 20 μm; if it is thinner than 5 μm, the charging potential will be low, making it impossible to obtain a sufficient density of the copied image. Moreover, if it is thicker than 50 urrt, it is not preferable in terms of productivity.

This a-C film has high light transmittance, high dark resistance, and is rich in charge transport properties, and even if the film thickness is 5 μm or more as mentioned above, carriers are transported without being trapped and contribute to bright attenuation. is possible.

In the process of forming a-CM from the raw material gas in the present invention, the most suitable method is to form the raw material gas through a plasma state that can be generated by a plasma method using direct current, low frequency, high frequency, microwave, etc. Although preferred, it may also be formed through an ion state generated by ionization vapor deposition, ion beam vapor deposition, etc., or from neutral particles generated by vacuum vapor deposition, sputtering, etc. or a combination thereof.

In the present invention, in addition to hydrocarbons, a -CIl! Oxygen compounds are used to add at least oxygen atoms to J. The phase state of the oxygen compound does not necessarily have to be a gas phase at room temperature and normal pressure; it can be used in either a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It is. Examples of oxygen compounds include inorganic compounds such as oxygen, ozone, water vapor, -carbon oxide, carbon dioxide, carbon dioxide, and hydroxyl groups (-O
H), aldehyde group (-COH), acyl) It group (
RCO-, -CRO), ketone group (>Co), ether bond (-〇-), ester bond (-Coo-),
Organic compounds having functional groups or bonds such as heterocycles containing oxygen are used. As the organic compound having a hydroxyl group, for example, methanol, ethanol, propatool, butanol, furyl alcohol, fluoroethanol, fluorobutanol, phenol, cyclohexanol, benzyl alcohol, furfuryl alcohol, etc. are used. Examples of organic compounds having an aldehyde group include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal,
Acrolein, benzaldehyde, furfural, etc. are used. Examples of organic compounds having an acyl group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, valmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, toluic acid, salicylic acid,
Cinnamic acid, naphthoic acid, phthalic acid, furanic acid, etc. are used. Examples of organic compounds having a ketone group include acetone, ethyl methyl ketone, methyl propyl ketone, butyl methyl ketone, binacolon, diethyl ketone, methyl vinyl ketone, mesityl oxide, methylhebutenone, cyclobutanone, cyclopentanone, cyclohexanone, Acetophenone, propiophenone, butyrophenone, parellophenone, dibenzylketone, acetonaphthone, acetochenone, acetofuron, etc. are used. Examples of organic compounds having an ether bond include methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, ethyl methyl ether, methyl propyl ether, methyl butyl ether, methyl amyl ether, ethyl propyl ether,
Ethyl butyl ether, ethyl amyl ether, vinyl ether, allyl ether, methyl vinyl ether, methyl furyl ether, ethyl vinyl ether, ethyl furyl ether, anisole, phenetol, phenyl ether, benzyl ether, phenylbenzyl ether, naphthyl ether, ethylene oxide, propylene oxide,
Trimethylene oxide, tetrahydrofuran, tetrahydrobilane, dioxane, etc. are used. Examples of organic compounds having an ester bond include methyl formate, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl propionate, ethyl propionate, and propion. Propyl acid, butyl propionate, amyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, amyl butyrate, methyl valerate, ethyl valerate,
Propyl valerate, butyl valerate, amyl valerate, methyl benzoate, ethyl benzoate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, methyl salicylate, ethyl salicylate, propyl salicylate, butyl salicylate,
Amyl salicylate, methyl anthranilate, ethyl anthranilate, butyl anthranilate, amyl anthranilate, methyl phthalate, ethyl phthalate, butyl phthalate, and the like are used. Examples of heterocyclic compounds containing oxygen include furan, oxazole, furazane, pyran, oxazine, morpholine, benzofuran, pandioxazole,
Chromene, chromane, dibenzofuran, xanthine, phenoxazine, oxolane, dioxolane, oxathiolane, oxadiazine, benzisoxazole, etc. are used.

In the present invention, the amount of oxygen atoms contained as a chemical modifier is 7. ○It is less than atomic%. Here, the content of oxygen atoms in the film can be determined by a conventional method of elemental analysis, such as Auger analysis. When the amount of oxygen atoms is higher than 7.0 at%, the oxygen atoms, which ensured suitable transport properties when added in small amounts, exhibit an effect that increases the resistance of the film, causing an increase in the residual potential. . In addition, some oxygen source gases, such as oxygen gas, ozone gas, -
Carbon oxide gas has a strong etching effect, and if you try to increase the amount of oxygen atoms added to the film by increasing the flow rate, the film formation rate will decrease and a certain amount of film thickness will be required. This is inconvenient in forming a charge transport layer. Therefore, the range of the amount of oxygen atoms added in the present invention is important.

In the present invention, the amount of oxygen atoms contained as a chemical modifier can be controlled mainly by increasing or decreasing the amount of the aforementioned oxygen compound introduced into the reaction chamber in which the plasma reaction is performed. If the amount of oxygen compound introduced is increased,
It is possible to increase the amount of oxygen atoms added into the a-C film according to the present invention, and conversely, if the amount of oxygen compounds introduced is reduced, the amount of oxygen atoms added into the a-C film according to the present invention can be increased. It is possible to add a small amount.

In the present invention, silane gas, disilane gas, or fluorinated silane gas is used to form the a-3i film. Furthermore, phosphine gas or diborane gas is used as a raw material gas for incorporating phosphorus atoms or boron atoms as chemical modifiers into the film. Furthermore, germane gas is used to contain germanium atoms.

The content of germanium atoms contained in the a-Si film in the present invention is preferably 30 at % or less based on the total of silicon atoms and germanium atoms. Here, the contents of germanium atoms and silicon atoms can be determined by a conventional method of elemental analysis, for example, Auger analysis. The content of germanium atoms can be increased by increasing the flow rate of germane gas flowing during film formation. As the content of germanium atoms increases, the long wavelength sensitivity of the photoreceptor of the present invention improves, and the exposure source can be selected from a wide range from the short wavelength region to the long wavelength region, which is preferable. Excessive addition is not preferable since a larger content will result in a decrease in charging ability. Therefore, the content of germanium atoms contained in a-5iyc in the present invention is important.

In the present invention, the amount of phosphorus atoms or boron atoms contained as a chemical modifier is 20,000 atomic ppm or less based on all constituent atoms. Here, the content of phosphorus atoms or boron atoms in the film is determined by a conventional method of elemental analysis, such as Auger analysis or I
This can be known through MA analysis. When the content of phosphorus atoms or boron atoms in the film is higher than 200 atoms ppm,
Phosphorus atoms or boron atoms, which, when added in small amounts, ensure suitable transport properties or polarity control effects, conversely exhibit the effect of lowering the resistance of the film, resulting in a decrease in charging ability. Therefore, the range of the amount of phosphorus atoms or boron atoms added in the present invention is important.

The amount of hydrogen atoms or fluorine atoms contained in the a-Si film of the present invention is necessarily determined from the manufacturing aspect of using glow discharge, but the total amount of silicon atoms and hydrogen atoms or silicon atoms and fluorine atoms On the other hand, the content can be approximately 10 to 35 at%. Here, the content of hydrogen atoms or fluorine atoms in the film can be determined by using conventional methods of elemental analysis, such as ◯NH analysis and Auger analysis.

The appropriate thickness of the a-Si film as the charge generation layer in the present invention is 0.1 to 5 μm for use in a normal electrophotographic process, and if it is thinner than 0.1 μm, light absorption is insufficient. As a result, sufficient charge generation is not performed, resulting in a decrease in sensitivity. Moreover, if it is thicker than 5 μm, it is not preferable in terms of productivity. This a-Si film has a rich charge generation ability,
Furthermore, in the laminated structure with the a-C film, which is the most characteristic feature of the present invention, generated carriers can be efficiently injected into the a-C film, contributing to suitable bright attenuation.

The process of forming the a-3i film from the raw material gas in the present invention is carried out in the same manner as the case of forming the a-C film.

In the present invention, the amount of phosphorus atoms or boron atoms contained as a chemical modifier can be controlled mainly by increasing or decreasing the amount of the aforementioned phosphine gas or diborane gas introduced into the reaction chamber in which the plasma reaction is performed. is possible. If the amount of phosphine gas or diborane gas introduced is increased,
It is possible to increase the amount of phosphorus atoms or boron atoms added to the a-Si film according to the present invention, and conversely, if the amount of phosphine gas or diborane gas introduced is reduced, the a-Si film according to the present invention It is possible to reduce the amount of phosphorus atoms or boron atoms added into the film.

It is optimal for the photoreceptor in the present invention to have a functionally separated structure consisting of a charge generation layer and a charge transport layer, and the laminated structure of the charge generation layer and the charge transport layer may be appropriately selected as necessary. is possible.

FIG. 1 shows, as one embodiment, a structure in which a charge transport layer (2) and a charge generation layer (3) are sequentially laminated on a conductive substrate (1). FIG. 2 shows, as another embodiment, a structure in which a charge generation layer (3) and a charge transport layer (2) are sequentially laminated on a conductive substrate (1). FIG. 3 shows, as another embodiment, a charge transport layer (2), a charge generation layer (3), and a charge transport layer (2) on a conductive substrate (1).
This figure shows a structure in which these are sequentially laminated.

When the surface of the photoreceptor is positively charged using a corona charger or the like and then used for image exposure, in FIG. 1, holes generated in the charge generation layer (3) pass through the charge transport layer (2). In the second rM, electrons generated in the charge generation layer (3) travel toward the surface of the photoreceptor in the charge transport layer (2), and in FIG. The holes generated in step (3) travel toward the conductive substrate (1) through the charge transport layer (2) on the conductive substrate side, and at the same time, the electrons generated in the charge generation layer (3) travel toward the conductive substrate (1) in the charge transport layer (2) on the conductive substrate side. The charge transport layer (2) travels toward the photoreceptor surface, forming a static latent image with proper brightness attenuation. On the other hand, when the photoreceptor surface is negatively charged and then used by image exposure,
The mobility of carriers can be understood by exchanging the behavior of electrons and holes. In FIGS. 2 and 3, the irradiation light for image exposure passes through the charge transport layer, but since the charge transport layer according to the present invention has excellent translucency, it forms a suitable latent image. Is possible.

FIG. 4 shows a conductive substrate (1), a charge transport layer (2), a charge generation layer (3) and a surface protective layer (
4) is shown in a structure formed by sequentially stacking them. In other words, it corresponds to the form shown in Fig. 1 with a surface protective layer provided, but
In the form of FIG. 1, since the outermost surface is an a-5i film with poor moisture resistance, in many cases it is preferable to provide a surface protective layer to ensure practical humidity stability. Second
In the case of the configurations shown in Figures and Figure 3, the outermost surface is a with excellent durability.
- Since it is a C film, there is no need to provide a surface protective layer, but for the purpose of adjusting the consistency with various elements in the copying machine, such as preventing stains on the surface of the photoreceptor due to adhesion of developer, surface protection Providing layers can also be an alternative form.

FIG. 5 shows an intermediate layer (5), a charge generation layer (3), and a charge transport layer (2) on a conductive substrate (1) as a rough form.
This figure shows a structure in which these are sequentially laminated. That is, the second
This corresponds to the form shown in the figure with an intermediate layer provided, but in the form shown in Fig. 2, the bonding surface with the conductive substrate is an a-Si film, which ensures adhesiveness and injection blocking effect in most cases. It is preferable to provide an intermediate layer for this purpose. In the case of the configurations shown in FIGS. 1 and 3, since the bonding surface with the conductive substrate is the charge transport layer according to the present invention, which has excellent adhesiveness and injection blocking effect, it is not necessary to provide an intermediate layer. For example, an intermediate layer may be provided for the purpose of adjusting compatibility with a manufacturing process before forming a photosensitive layer, such as a pretreatment method for a conductive substrate.

FIG. 6 shows, as a rough form, an intermediate layer (5), a charge transport layer (2), and a charge generation layer (3) on a conductive substrate (1).
This figure shows a structure in which a surface protection layer (4) and a surface protection layer (4) are sequentially laminated. That is, it corresponds to the form shown in FIG. 1 with an intermediate layer and a surface protective layer provided.

The reason for providing the intermediate layer and the surface protective layer is the same as described above, and therefore, providing the intermediate layer and the surface protective layer in the configurations shown in FIGS. 2 and 3 can be an alternative form.

In the present invention, the intermediate layer and the surface protective layer are not particularly limited in terms of material or manufacturing method, and can be appropriately selected as long as a predetermined purpose can be achieved. An a-C film according to the invention may also be used. However, if the material used is, for example, an insulating material as described in the conventional example, the film thickness must be kept at 5 μm or less to prevent generation of residual potential.

The charge transport layer of the photoreceptor according to the present invention decomposes molecules in the gas phase by discharge under reduced pressure, and diffuses active neutral or charged species contained in the generated plasma atmosphere onto the substrate, using electric force or It is preferable that the material be generated by a so-called plasma polymerization reaction, which is induced by magnetic force or the like and deposited as a solid phase by a recombination reaction on a substrate.

FIG. 7 shows a photoconductor manufacturing apparatus according to the present invention, and in the figure (701) to (706) are first to sixth tanks in which the raw material compound and carrier gas, which are in a gas phase at room temperature, are sealed, respectively. The tanks are the first to sixth control valves (707)
~(712) and the first to sixth flow rate controls! (713)～(
718). (719) to (721) in the figure
) are first to third containers containing raw material compounds that are in a liquid or solid phase at room temperature, and each container is heated to the first to third temperatures m! for vaporization. (722) to (724), each container is roughly connected to the seventh to ninth control valves (725) to (727) and the seventh to ninth flow control valves M (724).
28) to (730). These gases are mixed! After being mixed at (731), Lord! (732) into the reaction chamber (733). The pipes along the way are heated appropriately to prevent the vaporized gas from the raw material compound, which is in a liquid or solid state at room temperature, from condensing on the way! (734), heating is possible. A ground electrode (735) and a power application electrode (736) are installed facing each other in the reaction chamber, and each electrode can be heated by electrode heating M (737). The power application 1!1 (736) is equipped with a matching box for high frequency power (738
) are connected to a high frequency power source (739), a low frequency power source (741) is connected to a low frequency power matching box (740), and a DC power source (743) is connected to a low pass filter (742). Power with different frequencies can be applied by a switch (744). Reaction chamber (733
) can be adjusted by a pressure control valve (745), and the pressure in the reaction chamber (733) can be reduced by an exhaust system selection valve (74).
6), diffusion pump (747), oil rotary pump (
748), or cooling exclusion device (749), mechanical booster pump (750), oil rotary pump (74)
8). The exhaust gas is made safe and harmless by a suitable exclusion device (753) and then exhausted into the atmosphere. These exhaust system piping can also be heated and cleaned by appropriately placed piping heaters (734) to prevent the vaporized gas from the raw material compound, which is in a liquid or solid phase state at room temperature, from condensing on the way. ing. The reaction chamber (733) also has a reaction chamber heater (751) for the same reason.
A conductive substrate (752) is installed on the electrodes arranged inside. In FIG. 7, the conductive substrate (752) is fixedly arranged on the ground electrode (735), but it may also be fixedly arranged on the power application electrode (738), or even roughly arranged on both sides. good.

FIG. 8 shows another embodiment of the photoconductor manufacturing apparatus according to the present invention, which is similar to the photoconductor manufacturing apparatus according to the present invention shown in FIG. 7 except for the internal configuration of the reaction chamber (833). can be,
The numbers that have been added can be understood by replacing the numbers in the 700s with numbers in the 800s. In FIG. 8, the reaction chamber (83
3) A cylindrical conductive substrate (852) that also serves as the ground electrode (735) in FIG. 7 is installed inside, and an electrode heater (837) is placed inside. Conductive substrate (
852) Around the same cylindrical power application 1! f
i+ (836), and an electrode heater (837) is placed on the outside.
) are distributed. The conductive substrate (852) is rotatable using an external drive motor (854).

The reaction chamber used for photoreceptor production is preliminarily heated by a diffusion pump.
The pressure is reduced to about 0-4 to 10 Torr, and the degree of vacuum is checked and the gas adsorbed inside the device is desorbed. At the same time, an electrode heater heats the electrode and the conductive substrate fixedly disposed on the electrode to a predetermined temperature. If necessary, an undercoat layer or a charge generation layer may be provided in advance on the conductive substrate in order to obtain a desired photoreceptor structure from among those described above. The present apparatus or a separate apparatus may be used to provide the undercoat layer or the charge generation layer. Next, the raw material gases are introduced into the reaction chamber from the first to sixth tanks and the first to third containers while being kept at a constant flow using the first to ninth flow rate controllers, and the inside of the reaction chamber is controlled by the pressure control valve. Maintain constant vacuum. After the gas flow rate is stabilized, a connection selection switch is used to select, for example, a high frequency power source, and high frequency power is applied to the power application electrode. A discharge is started between the two electrodes, and a solid phase film is formed on the substrate over time. The a-Si film or a-CM can be formed arbitrarily by changing the raw material gas. Films with different compositions can be laminated by once stopping the discharge, changing the source gas composition, and then restarting the discharge. It is also possible to gradually change only the raw material gas flow rate while sustaining the discharge, and to stack films of different compositions with a gradient.

The film thickness is controlled by the reaction time, and when a predetermined film thickness and laminated structure are reached, the discharge is stopped to obtain a photoreceptor according to the present invention. Next, the first to ninth vH control valves are closed to sufficiently exhaust the inside of the reaction chamber. If the desired photoreceptor configuration is obtained, the vacuum in the reaction chamber is broken and the photoreceptor according to the present invention is taken out from the reaction chamber. Furthermore, if a charge generation layer or an overcoat layer is required in the desired photoreceptor configuration, this device can be used as is, or these layers can be removed by breaking the vacuum and transferring to another device. to obtain a photoreceptor according to the present invention.

The present invention will be described below with reference to Examples.

Great Journey 51 Using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

Charge transport layer forming step: In the glow discharge decomposition device shown in FIG. 7, first, the inside of the reaction device (733) is brought to a high vacuum of about 10'' Torr, and then the third control valve (709) is opened. Release the third
Output pressure of oxygen gas from tank (703) is 1.0Kg/c
It was made to flow into the third flow rate control @J vessel (715) under m2. At the same time, myrcene gas is supplied from the first container (719) to the first
Under temperature controller (722) temperature of 50°C, the seventh flow rate controller (7
28) It was allowed to flow into the interior. Oxygen gas flow rate is 4sccmq
And set the flow rate of myrcene gas to 20 seconds and mix in the middle! (731), main pipe (732)
) into the reaction chamber (733).

After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 1.5 Torr. On the other hand, as the conductive substrate (752), tI
Using an aluminum substrate of i50 x width 50 x 3 mm thick, preheat it to 150°C, and with the gas flow rate and pressure stable, connect it to the low frequency power source (741) using the connection selection switch (744). ), and apply a power of 120 Watts to the power application electrode (736) at a frequency of 35
A plasma polymerization reaction was performed for about 2 hours and 40 minutes by applying a voltage of KHz, and a 15 μm thick a
-C film was formed as a charge transport layer.

After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

When organic elemental analysis was performed on the a-C film obtained as described above, the amount of hydrogen atoms contained was 47 at % based on the total amount of carbon atoms and hydrogen atoms. Moreover, the amount of oxygen atoms contained was 0.7 at % based on the total constituent atoms according to Auger analysis.

Charge generation layer forming step: Next, some of the tanks were replaced, and the first control valve (7o7)
The second control valve (708) and the sixth control valve (712) are released, hydrogen gas is supplied from the first tank (701), Germanic gas is supplied from the second tank (702), and the sixth tank (706
) under an output pressure of IKg/cm2.
, second, and sixth flow rate regulators (713, 714, and 7
18) Don't let it flow inside. At the same time, the fourth control valve (710)
was released and heated to 10O with hydrogen gas from the fourth tank (704).
Diborane gas diluted to ppm is output at an output pressure of 1°5 kg.
/cm2 into the fourth flow controller (716). Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 200 sec, the flow rate of germane gas to 6 sccm, the flow rate of silane gas to 11008 cc, and the flow rate of hydrogen gas to 1100 cc.
The flow rate of the diborane gas diluted to pp was set to 10105e, and the diborane gas was allowed to flow into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 1.0T.
The pressure control valve (745) was adjusted so that the

On the other hand, a conductive substrate (752) on which an a-C film is formed
is heated to 240°C, and when the gas flow rate and pressure are stable, the frequency is 13.5 from the high frequency power supply (739).
40Watt to the power application electrode (736) under 6MHz
electric power was applied to generate a glow discharge. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-3i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 18 at.% of the total constituent atoms, and the boron atoms were 10 at.ppm.
, germanium atoms were 9.7 at%.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -490V (+480V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 32 V/.mu.m (31 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 12 seconds (approximately 13 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, white light was used to attenuate the surface potential to 20% of the highest charging potential.The amount of light required was 1.3 lux·sec (1.2 lux・seconds), and from this it was understood that it had sufficient photosensitivity performance. Also, after initial charging to the highest charging potential, what was the amount of light required to attenuate the surface potential to 20% of the highest streetcar potential using semiconductor laser light (emission wavelength: 780 nm)? ,3
erg/cm2 (7, lerg/cm2), and from this it was understood that it had sufficient long wavelength light sensitivity performance.

From the above, it can be understood that the photoreceptor according to the present invention shown in this example has excellent performance as a photoreceptor.

Further, when an image was formed and transferred to this photoreceptor using the commonly used Carlson process, a clear image was obtained.

As shown in FIG. 1, using the manufacturing apparatus according to the present invention,
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided on the head.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. 7, first, the inside of the reaction apparatus (733) was brought to a high vacuum of about 10-6 Torr, and then the third control valve (709) was released. , the output pressure of nitrous oxide gas from the third tank (703) is 1.0Kg/
am2 into the third flow controller (715). At the same time, styrene gas is poured into the first container from the first container (719).
Under temperature controller (722) temperature of 30°C, the seventh flow rate controller (7
28) It was allowed to flow into the interior. The flow rate of nitrous oxide gas is 15 seconds.
The flow rates of CCm and styrene gas were set to 45 sec, and they flowed into the reaction chamber (733) from the main pipe (732) via the intermediate mixing M (731). After each flow rate stabilizes, the pressure inside the reaction chamber (733) becomes L.
The pressure regulating valve (745) was adjusted to 8 Torr. On the other hand, as the conductive substrate (752),! Using an aluminum substrate of 50 x width 50 x 3 mm thickness, 15
After heating the gas to 0°C and stabilizing the gas flow rate and pressure, turn on the low frequency power supply (741) that was previously connected using the connection selection switch (744), and connect the power application electrode (744).
36) was applied with a power of 130 Watt at a frequency of 40 KHz to carry out a plasma polymerization reaction for about 1 hour and 15 minutes,
A 15 μm thick a-C film was formed as a charge transport layer on a conductive substrate (752). After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

When organic elemental analysis was performed on the a-C film obtained as described above, the amount of hydrogen atoms that could be contained was 42 at % based on the total amount of carbon atoms and hydrogen atoms. Moreover, the amount of oxygen atoms contained was 1.9 at % based on the total constituent atoms according to Auger analysis.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
The second N-node valve (708) and the sixth control valve (712) are released, hydrogen gas is supplied from the first tank (701), Germanic gas is supplied from the second tank (702), and the sixth tank (70
6), silane gas was flowed into the first and sixth flow rate control plugs (713 and 718) under an output pressure of IKg/cm2. At the same time, the fourth control valve (710) is opened, and phosphine gas diluted to 1100 pp with hydrogen gas is supplied from the fourth tank (704) to the fourth flow rate controller (716) under an output pressure of 1.5 kg/cm2. I let it flow inside. Adjust the scale of each flow rate control type to adjust the hydrogen gas flow rate to 200 s.
e c m 1 germane gas flow rate 68 CC mN silane gas flow rate 101005 e.

The flow rate of phosphine gas diluted to 1100 pp with hydrogen gas was set to 10105e, and the gas was allowed to flow into the reaction chamber (733). After each flow rate stabilizes, the reaction chamber (733
) so that the pressure in the pressure control valve ( ) becomes 0.8 Torr
745) was adjusted.

On the other hand, a conductive substrate (752) on which an a-C film is formed
is heated to 250°C, and when the gas flow rate and pressure are stable, the frequency is 13.5 from the high frequency power supply (739).
40Watt to the power application electrode (736) under 6MHz
electric power was applied to generate a glow discharge. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-3i film was subjected to ONH analysis in metal (WtJ
% Seisakusho 1i1EMGA-1300), t-ditechnical analysis, and IMA analysis, it was found that the contained hydrogen atoms were 20 at %, the phosphorus atoms were 11 at ppm, and the germanium atoms were 10 at %. Met.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -470V (+720V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 31 V/.mu.m (47 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to a surface potential of 9% of Vmax in the dark was approximately 18 seconds (approximately 28 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using white light.The amount of light required was 1.4 lux sec (2.9 lux・seconds), and from this it was understood that it had sufficient photosensitivity performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using semiconductor laser light (emission wavelength 780 nm), and the amount of light required was 8. Oe
rg/am2 (13.2 erg/cm2), and from this it was understood that it had sufficient long wavelength light sensitivity performance.

From the above, it can be understood that the photoreceptor according to the present invention shown in this example has excellent performance as a photoreceptor.

Further, when an image was formed and transferred to this photoreceptor using the commonly used Carlson process, a clear image was obtained.

Using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. 707,708
, and 709), and hydrogen gas is supplied from the first tank (701), ethylene gas from the second tank (702), and oxygen gas from the third tank (703) at an output pressure of 1.0.
The first, second and third flow controllers (under Kg/am2)
713, 714, and 715). Then, adjust the scale of each flow rate controller to increase the hydrogen gas flow rate to 60
sec, the flow rate of ethylene gas was set to 60 scm1, and the flow rate of oxygen gas was set to 10105e, and flowed into the reaction chamber (733) from the main pipe (732) via an intermediate mixer (731). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 2.2 Torr. On the other hand, the conductive substrate (752) is t71150x width 50x thickness 3m
Using an aluminum substrate of M, preheat it to 250°C, and with the gas flow rate and pressure stable, turn on the high frequency power supply (739) connected in advance with the connection selection switch (744), and turn on the power. A power of 150 Watts was applied to the medium voltage ai (736) at a frequency of 13.56 MHz to carry out a plasma polymerization reaction for about 3 hours, and a 15 μm thick a-C film was transferred on the conductive substrate (752) for charge transport. Formed as a layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 39 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of oxygen atoms was 3.0 at % based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
The second control valve (708), the third control valve (709), and the sixth control valve (712) are released, hydrogen gas is released from the first tank (701), tetrafluorosilane gas is removed from the second tank (702), Germanic gas from the third tank (702) and the sixth
Silane gas is supplied from the tank (706) at an output pressure of IKg/c.
The first, second, third, and sixth flow controllers (7
13,714,715, and 718).

At the same time, the fourth control valve (710) is released and the fourth tank (
704), the diborane gas diluted to 1100 pp with hydrogen gas is allowed to flow into the fourth flow limiter (716) under an output pressure of 1°5 Kg/cm2. Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 200 scCm, the flow rate of silane tetrafluoride gas to 50 seconds, and the flow rate of germane gas to 6 seconds.cc rn% Silane gas flow rate to 50 seconds.
ecm.

The flow rate of diborane gas diluted to 1100pp with hydrogen gas was set to 10105e, and the reaction chamber (7
33). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 0°9 Torr. On the other hand, the conductive substrate (752) on which the a-C film has been completely formed is heated to 230°C, and with the gas flow rate and pressure stable, it is heated at a frequency of 13.56 MHz from a high frequency power source (739). A power of 3!5 Watts was applied to the power application electrode (736) to generate glow discharge. Do this discharge for 5 minutes,
A charge generation layer having a thickness of 0.3 μm was obtained.

The obtained a-3i film was subjected to ONH analysis in metal (Full EMGA-1300 manufactured by Itaba), Auger analysis, and I
According to MA analysis, the hydrogen atoms that can be contained are 24 at% of the total constituent atoms, and the boron atoms are 10 atoms PPm.
The content of 5 fluorine atoms was 5 at%, and the content of germanium atoms was 10.5 at%.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -760V (+770V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 49 V/.mu.m (51 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 35 seconds (approximately 43 seconds).
seconds), and from this we can understand that it has sufficient charge retention performance. Furthermore, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential, and the amount of light required was 3.4 lux · seconds (3.6 lux · seconds), and from this it was understood that it had sufficient photosensitivity performance.

From the above, it is understood that the photoreceptor according to the present invention shown in this example has excellent performance as a photoreceptor.

Further, when an image was formed and transferred to this photoreceptor using the commonly used Carlson process, a clear image was obtained.

By using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were clearly provided.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Valve (707,
708 and 709), and the first tank (701)
Hydrogen gas from the second tank (702), butadiene gas from the third tank (703), and oxygen gas from the third tank (703) are supplied to the first, second, and third flow rate controllers (713, 714 and 715).

The flow rate of hydrogen gas was set to 90 seconds, the flow rate of butadiene gas was set to 70 seconds, and the flow rate of oxygen gas was set to 18 seconds, via an intermediate mixer (731),
It flowed into the reaction chamber (733) from the main pipe (732). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 2.2 Torr.

On the other hand, as the conductive substrate (752),
Using an aluminum substrate with a thickness of 3 mm, heat it to 120℃ in advance.
After heating to , and with the gas flow and pressure stable,
Turn on the low frequency power supply (741) that has been connected in advance using the connection selection switch (744), and connect the power application electrode (736).
) was applied with a power of 100 Wa 11 at a frequency of 500 KH 2 to carry out a plasma polymerization reaction for about 30 minutes to form a 15 μm thick a-C film as a charge transport layer on the conductive substrate (752). After completing the film formation, stop applying power and
The control valve was closed and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 55 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of oxygen atoms was 4.8 at% based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
The second control valve (708), the third control valve (709), and the sixth control valve (712) are released, hydrogen gas is released from the first tank (701), tetrafluorosilane gas is removed from the second tank (702), Germanic gas from the third tank (703) and the sixth
Silane gas is supplied from the tank (706) at an output pressure of I K g.
/Cm2 into the first, second, third, and sixth flow controllers (713, 714, 715, and 718). At the same time, the fourth control valve (710) is released and the fourth control valve (710) is released.
Phosphine gas diluted to 1100 pp with hydrogen gas from the tank (704) was allowed to flow into the fourth flow rate suppressor (716) under an output pressure of 1.5 kg/cm2. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec.
, the flow rate of the germane gas was 6 sec, the flow rate of the tetrafluorosilane gas was 50 s c cm %, and the flow rate of the silane gas was 50 sec.

The flow rate of phosphine gas diluted to 1100 pp with hydrogen gas was set to 10105e, and the gas was allowed to flow into the reaction chamber (733). After each flow rate stabilizes, the reaction chamber (733
) so that the pressure in the pressure control valve ( ) becomes 0.8 Torr
745) was adjusted.

On the other hand, a conductive substrate (752) on which an a-C film is formed
is heated to 240°C, and when the gas flow rate and pressure are stable, the frequency is 13.5 from the high frequency power supply (739).
40Watt to the power application electrode (736) under 6MHz
electric power was applied to generate a glow discharge. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-Si film was subjected to ONH analysis in metal (Full EMGA-1300 manufactured by Itaba), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 26 atomic% and the phosphorus atoms were 13 atomic ppm% of the total constituent atoms.
The content of fluorine atoms was 5.6 at%, and the content of germanium atoms was 9.8 at%.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -680V (+990V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 44 V/.mu.m (64 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 47 seconds (approximately 50%
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using white light, and the required amount of light was 3.6 lux · seconds (8.1 lux · seconds), and from this fact it was understood that the film had sufficient photosensitivity performance.

From the above, it is understood that the photoreceptor according to the present invention shown in this example has excellent performance as a photoreceptor.

Further, when an image was formed and transferred to this photoreceptor using the commonly used Carlson process, a clear image was obtained.

Using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. 707,70
8, and 7o9), hydrogen gas from the first tank (701), acetylene gas from the second tank (702),
and oxygen gas from the third tank (703) at an output pressure of 1
．． 1st, 2nd, and 3rd flow rate control a under 0Kg/cm2
! It was made to flow into the I vessels (713, 714, and 715).

Then, adjust the scales of each flow rate control type to set the hydrogen gas flow rate to 88 seconds and the acetylene gas flow rate to 45 seconds.
, and the flow rate of oxygen gas is set to 24 seconds, and the main pipe (732) is passed through an intermediate mixer (731).
The liquid then flowed into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 2.0 Torr.
The pressure control valve (745) was adjusted so that on the other hand,
The conductive substrate (752) is 50 fir x 50 x thickness 3
Using an aluminum substrate with a diameter of 1 to the application electrode (736)
A plasma polymerization reaction was performed for about 4 hours and 40 minutes by applying a power of 0.00 Watt at a frequency of 4 MHz, and the conductive substrate (
752) A 15 μm thick a-C film was formed thereon as a charge transport layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 30 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of oxygen atoms was 6.1 at% based on the total constituent atoms.

Charge generation layer forming step: Next, in the same manner as in Example 2, a charge generation layer of a photoreceptor according to the present invention was formed.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -660V (+960V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 43 V/.mu.m (63 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 35 seconds (approximately 42
seconds), and from this we can understand that it has sufficient charge retention performance. In addition, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential.The amount of light required was 5.2 lux·sec (11.5 lux・seconds), and from this we can understand that it has sufficient photosensitivity performance.

From the above, it is understood that the photoreceptor according to the present invention shown in this example has excellent performance as a photoreceptor.

Further, when an image was formed and transferred to this photoreceptor using the commonly used Carlson process, a clear image was obtained.

[Brief explanation of the drawing]

1 to 6 are drawings showing the structure of a photoreceptor according to the present invention, and FIGS. 7 to 8 are drawings showing an apparatus for manufacturing a photoreceptor according to the invention. Applicant: Minolta Camera Co., Ltd. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Procedural Amendment October 21, 1988

Claims (1)

[Claims] In a functionally separated photoreceptor having a charge generation layer and a charge transport layer, the charge transport layer is a hydrogenated amorphous carbon film containing at least oxygen atoms, and the charge generation layer contains phosphorus atoms and boron atoms. A photoreceptor characterized in that it is a hydrogenated amorphous silicon germanium film containing at least one of phosphorus atoms and boron atoms, or a fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms.