JPS6382459A - Photosensitive body - Google Patents

Abstract

PURPOSE:To improve the transferability of an electric charge transfer layer by using the charge transfer layer consisting of hydrogenated amorphous carbon contg. oxygen and halogen and an electric charge generating layer. CONSTITUTION:For example, the charge transfer layer 2 and the charge generating layer 3 are successively laminated on a conductive substrate 1. The layer 2 consists of the hydrogenated amorphous carbon film contg. at least the oxygen and halogen. The layer 3 consists of the hydrogenated or fluorinated amorphous silicon germanium film. The layers 2, 3 can be formed by glow discharge. The charge transfer layer having the adequate transferability and excellent electric chargeability, durability, etc., is thereby obtd. The charge generating layer which has excellent photoconductivity and the functions of which can be best utilized in spite of the reduction in the thickness thereof is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a photoreceptor having a charge generation layer and a charge transport layer.

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

The main electrophotographic photoreceptor materials conventionally used include inorganic substances such as amorphous selenium, selenium arsenide, selenium tellurium, cadmium sulfide, lead 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. Furthermore, since amorphous silicon originally has a high dielectric constant, it has poor charging performance, 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. It has to be deposited.

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.
Plasma Pol
ymerization), 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 <10'6 Ωcm, like ordinary polyethylene films. or, at least, it was used with the understanding 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 thereon. ing. Japanese Patent Application Publication No. 5
Publication No. 9-38753 discloses that 10A to 100 high-resistance plasma polymerized films of 1013 to 1QI5Ωcm, which are generated from a mixed gas of oxygen, nitrogen, and hydrocarbons, are provided 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.

JP-A No. 60-63541 discloses a photoreceptor having a diamond-like carbon film of 200A to 2 μm as an adhesive layer in the middle in order to improve the adhesion between an aluminum substrate and an amorphous silicon layer provided thereon. is disclosed, and 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.
A photoreceptor is disclosed. 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 diamond-like carbon FIH9= of 500 to 2 μm as a surface protective layer,
From the viewpoint of light transmission, the film thickness is preferably 2 μm or less. In Japanese Patent Application Laid-open No. 60-249115, 0.05
A technique has been disclosed in which an amorphous carbon or hard carbon film with a thickness of about 5 .mu.m is used as a surface protective layer, and it is said that if the film thickness exceeds 5 .mu.m, the photoreceptor activity will be 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, 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 Recompa (P.

Philosophical Magazine published in 1976 by
Magazine) Volume 33, pages 935 to 94
Since it was reported on page 9 that it is a material whose polarity can be controlled, attempts have been made to apply it to various photoelectric devices. Regarding the application to photoreceptors, for example,
No. 62254, Japanese Patent Application Laid-open No. 119356/1983,
JP-A-57-177147, JP-A-57-119
357, JP 57-177149, JP 57-119357, JP 57-17714
Publication No. 6, JP-A-57-177148, JP-A-5
Amorphous silicon photoreceptors containing carbon atoms are disclosed in JP-A No. 7-174448, JP-A-57-174449, JP-A-57-174450, etc., but all of them are amorphous silicon photoconductors. The purpose is to adjust the properties using carbon atoms, and
Amorphous silicon itself requires a thick film.

71 As mentioned above, the plasma-based i-polymerized films conventionally used in electrophotographic photoreceptors have been used as so-called undercoat layers or overcoat layers; Organic polymer films are used based on the judgment that they are insulating and do not require the transport function of carriers.Therefore, they are only used as extremely thin films with a thickness of about 5 μm at most. is used only in thin films that pass through the film due to the tunnel effect, or if a tunnel effect cannot be expected, there is virtually no problem with the generation of residual potential.Furthermore, conventional electrophotography The amorphous silicon film used for this purpose is a so-called thick film, which has many disadvantages in terms of cost, productivity, etc.

While considering the application of amorphous carbon films to electrophotographic photoreceptors, the present inventors discovered that hydrogenated amorphous carbon films, which were originally thought to be insulating, contained oxygen atoms and halogen atoms. As a result, it has been found that when laminated with a hydrogenated or fluorinated amorphous silicon germanium film, it has charge transport properties and easily begins to exhibit suitable electrophotographic properties. Although the theoretical interpretation has many unclear points even for the present inventors, it is not possible to discuss it in detail. The band structure formed by electrons in stable energy states, such as π electrons, unpaired electrons, and residual free radicals, is similar to the band tlIt structure formed by hydrogenated or fluorinated amorphous silicon germanium in the conduction band or valence band. carriers generated in the hydrogenated or fluorinated amorphous silicon germanium film are easily injected into the hydrogenated amorphous carbon film containing oxygen atoms and halogen atoms. It is presumed that this is because the carriers can suitably travel through the hydrogenated amorphous carbon film containing oxygen atoms and halogen atoms due to the action of the electrons in the relatively unstable energy state described above.

By utilizing this new knowledge, the present invention solves all the above-mentioned essential problems of amorphous silicon photoreceptors, and also uses organic plasma polymerized films, especially oxygen It is an object of the present invention to provide a photoreceptor in which a hydrogenated amorphous carbon film containing atoms and halogen atoms is used as a charge transport layer, and a thin film of hydrogenated or fluorinated amorphous silicon germanium is used as a charge generation layer. purpose.

That is, the present invention provides a functionally separated photoreceptor having a charge generation layer and a charge transport layer, wherein the charge transport layer contains at least oxygen atoms and halogen atoms generated from a plasma polymerization reaction. It relates to a photoconductor characterized in that it is a hydrogenated amorphous carbon film, and the charge generation layer is a hydrogenated or fluorinated amorphous silicon germanium film (hereinafter, the charge transport layer according to the present invention is referred to as an a-C film and a hydrogenated amorphous silicon germanium film). The charge generation layer is referred to as an a-3i 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 and halogen atoms generated by glow discharge as a charge transport layer, and a hydrogenated amorphous carbon film containing at least oxygen atoms and halogen atoms generated by glow discharge as a charge generation layer. Alternatively, the present invention relates to a functionally separated photoreceptor characterized by being provided with a fluorinated amorphous silicon germanium film. Although the charge transport layer does not have clear photoconductivity for visible light or light with a wavelength near semiconductor laser light, it has suitable transport properties, and has excellent charging ability, durability, and weather resistance. It has excellent electrophotographic photoreceptor performance such as durability and environmental pollution resistance, and is also excellent in light transmission, so it provides an extremely high degree of freedom when forming a laminated structure as a function-separated photoreceptor. . In addition, the charge generation layer has excellent photoconductivity for visible light or light at a wavelength near the semiconductor laser tip, and is extremely thin 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, te°cane, unte°cane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane,
Normal paraffins such as octadecane, nonadecane, eicosane, heneicosane, tocosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, 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.
Isoparaffins such as 2.4-trimederpentane, 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-2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-
Olefins such as nonene, 1-decene, diolefins such as allene, methylalene, butadiene, bentadiene, hexadiene, cyclopentadiene, and triolefins such as ocimene, allocimene, myrcene, hexatriene, and , acetylene, butadiyne, 1゜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, bodocarbrene, mirene, and other terpenes, steroids, and the like are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimentene, 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.

Furthermore, other than hydrocarbons, any compound 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 at% of the total amount of carbon atoms and hydrogen atoms. . Here, the content of carbon atoms and hydrogen atoms in the film is determined by a conventional method of organic elemental analysis, for example, CN
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 thickness of 7 to 20 .mu.m is suitable for 0 .mu.m, and if it is thinner than 5 .mu.m, the charging potential will be low, making it impossible to obtain a sufficient copy image density. Moreover, if it is thicker than 50 μm, 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.

The process of forming an a-C film from a raw material gas in the present invention is a method in which the raw material gas is formed through a plasma state generated by a plasma method using direct current, low frequency, high frequency, or micro-waves. is the most preferable, but in addition, neutral particles may be formed through an ionic state that can be generated by ionization vapor deposition, ion beam vapor deposition, etc., or neutral particles generated by vacuum vapor deposition, sputtering, etc. It may be formed from a combination of these.

In the present invention, in addition to hydrocarbons, oxygen compounds can be used to add at least oxygen atoms into the a-C film. The phase state of the oxygen compound does not necessarily have to be a gas phase at room temperature and pressure; it can be used in either a liquid phase or the same phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. be. Examples of oxygen compounds include oxygen, ozone, water vapor, inorganic compounds such as carbon oxide, carbon dioxide, and carbon oxide, hydroxyl groups (-OH), aldehyde groups (-0OH), and acyl groups (RCO-, - C
R○), ketone group (>CO), ether bond (-〇-)
, ester bond (-COO-), heterocycle containing oxygen,
An organic compound having a functional group or bond such as the like is used. Examples of organic compounds having a hydroxyl group include methanol, ethanol, propatool, butanol, furyl alcohol, fluoroethanol, fluorobutanol, phenol, cyclohexanol, and benzyl alcohol.

Furfuryl alcohol, etc. are used. Examples of the organic compound having an aldehyde group include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, acrolein, benzaldehyde, and furfural. Examples of organic compounds having an acyl group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, palmitic 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,
Vinacolone, diethyl ketone, methyl vinyl ketone, mesityl oxide, methyl hebutenone, cyclobutanone,
Cyclopentanone, cyclohexanone, acetophenone, propiophenone, butyrophenone, valerophenone, dibenzyl ketone, 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, and ethyl amyl. Ether, vinyl ether, allyl ether, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, ethylfuryl ether, anisole, phenetol, phenyl ether, benzyl ether, phenylbenzyl ether, naphthyl ether, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydro Bilane, 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, butyrate.

propyl acid, 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. Examples of heterocyclic compounds containing oxygen include furan, oxazole, furazane, biran, oxazine, morpholine, benzofuran, benzoxazole, chromene, chroman, 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 7.0 at % or less based on all constituent atoms. 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 had ensured suitable transport properties when added in small amounts, conversely exhibit the effect of lowering the resistance of the film, resulting in a decrease in charging ability. will come. 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 film thickness will be required. This is inconvenient when 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 reduce the amount added.

In the present invention, in addition to hydrocarbons, halogen compounds are used to add at least halogen atoms to a-CH2. Here, the halogen atom refers to a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The phase state of the halogen 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 halogen compounds include fluorine, chlorine, bromine, iodine, hydrogen fluoride, chlorine fluoride, and JIS! Inorganic compounds such as element A, iodine fluoride, hydrogen chloride, bromine chloride, iodine chloride, hydrogen bromide, iodine bromide, hydrogen iodide, alkyl halides, aryl halides, styrene halides, polymethylene halides, etc. Organic compounds such as roform are used. Examples of the alkyl halide include methyl fluoride, methyl chloride, methyl bromide, methyl iodide, ethyl fluoride, ethyl chloride, ethyl bromide, ethyl iodide, propyl fluoride, propyl chloride, propyl bromide,
Propyl iodide, butyl fluoride, butyl chloride, butyl bromide, butyl iodide, amyl fluoride, amyl chloride, amyl bromide, amyl iodide, hexyl fluoride, hexyl chloride,
Hexyl bromide, hexyl iodide, hebutyl fluoride, hebutyl chloride, hebutyl bromide, hebutyl iodide, octyl fluoride, octyl chloride, octyl bromide, octyl iodide,
Nonyl fluoride, nonyl chloride, nonyl bromide, nonyl iodide, decyl fluoride, decyl chloride, decyl bromide, decyl iodide, etc. are used. As the aryl halide, for example, fluorobenzene, chlorobenzene, brombenzene, iodobenzene, chlorotoluene, bromotoluene, chlornaphthalene, bromnaphthalene, etc. are used. As the halogenated styrene, for example, chlorstyrene, bromustyrene, iodostyrene, fluorostyrene, etc. are used. Examples of halogenated polymethylene include methylene chloride, styrene bromide, methylene iodide, ethylene chloride, ethylene bromide, ethylene iodide, trimethylene chloride, trimethylene bromide, trimethylene iodide, butane dichloride, butane dibromide, Butane dichloride, pentane dichloride, pentane dibromide, pentane dichloride, hexane dichloride, hexane dibromide, hexane dichloride, hebutane dichloride, hebutane dibromide, hebutane dichloride, octane dichloride, Octane dibromide, octane shoide, nonane dichloride, nonane dibromide, decane dichloride, decane diiodide, etc. are used. As the heroborum, for example, fluoroform, chloroform, bromoform, iodoform, etc. are used.

In the present invention, the amount of halogen atoms that can be contained as a chemical modifier is 0.1 to 25 at.% based on the total constituent atoms. Here, the amount of halogen atoms contained in the film can be determined by a conventional method of elemental analysis, such as Auger analysis. If the amount of halogen atoms is lower than 0.1 atomic %, suitable charge transport properties are not necessarily guaranteed, and sensitivity decreases or residual potential is likely to occur, and
Sensitivity stability over time is also no longer guaranteed. When the amount of halogen atoms is higher than 25 atom%, the halogen atoms, which had guaranteed suitable charge transport properties and prevention of residual potential generation when added in an appropriate amount, could conversely cause a decrease in charging ability and It has the effect of lowering dark resistance, leading to a decrease in charge retention ability during storage for several months. Furthermore, film-forming properties are not necessarily guaranteed, leading to peeling of the film, oily state, or powdery state. Therefore, the range of the amount of halogen atoms added in the present invention is important.

In the present invention, the amount of halogen atoms contained as a chemical modifier can be controlled mainly by increasing or decreasing the amount of the halogen compound introduced into the reaction chamber in which the plasma reaction is performed.

By increasing the amount of halogen compound introduced, it is possible to increase the amount of halogen atoms added to the a-C film according to the present invention, and conversely, by decreasing the amount of halogen compound introduced, it is possible to increase the amount of halogen atoms added to the a-C film according to the present invention. It is possible to reduce the amount of halogen atoms added to the a-C film.

In the present invention, silane gas, disilane gas, or fluorinated silane gas is used to form a-5ily.

The amount of hydrogen atoms or fluorine atoms contained in the a-Sill in the present invention is necessarily determined from the manufacturing aspect of using glow discharge, but it is Approximately 10 to 35
Contains atomic%. Here, the content of hydrogen atoms or fluorine atoms in the film can be determined by using conventional methods of elemental analysis, such as ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, etc.

The appropriate thickness of the a-5i 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-5i film has a rich charge generation ability,
Furthermore, the most characteristic feature of the present invention is a-Cll!
In any laminated structure, it is possible to efficiently inject generated carriers into the a-C film and contribute to suitable bright attenuation.

The process of forming an a-Si film from a raw material gas in the present invention is carried out in the same manner as in the case of forming an a-C 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 with respect to 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 a wide range of exposure sources can be selected from the short wavelength region to the long wavelength region, which is preferable. Excessive addition is not preferable since a large content will lead to a decrease in charging ability. Therefore, the content of germanium atoms contained in the a-Si film in the present invention is important.

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 VI layer structure of the charge generation layer and the charge transport layer is appropriately selected as necessary. Is possible.

FIG. 1 shows, as one embodiment, a structure in which a charge transport IW (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 WI (2) are laminated one after the other on a conductive substrate (1). FIG. 3 shows, as another form, a structure in which a charge transport layer (2), a charge generation layer (3), and a charge transport layer (2) are sequentially laminated on a conductive substrate (1). It is something.

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 Figure 2, electrons generated in the charge generation layer (3) travel towards the photoreceptor surface in charge transport N (2), and in Figure 3, electrons are generated in the charge generation layer (3). The holes generated in the layer (3) travel toward the conductive substrate (1) through the charge transport N(2) on the conductive substrate side, and at the same time, the holes generate charge N(
The electrons generated in step 3) travel through the charge transport layer (2) on the front side towards the surface of the photoreceptor, thereby forming an electrostatic latent image guaranteed to have suitable flickering and decay. On the other hand, when the surface of the photoreceptor is negatively charged and then used for image exposure, the behavior of electrons and holes can be exchanged to understand the mobility of carriers. 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) with a charge transport layer (2), a charge generation layer (3) and a surface retaining layer as a rough form.
This figure shows a structure in which (4) are sequentially laminated. In other words, it corresponds to the form in which a surface protective layer is provided in the form shown in Fig. 1, but in the form shown in Fig. 1, the outermost surface is a-3i with poor moisture resistance.
Since it is a film, in many cases it is preferable to provide a surface protective layer to ensure practical humidity stability. In the case of the configurations shown in FIGS. 2 and 3, since the outermost surface is made of a-CM, which has excellent durability, there is no need to provide a surface protective layer. A further form of protection may be to provide a surface protective layer for the purpose of adjusting the compatibility with various elements within the copying machine.

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 a-Sil! Therefore, in many cases, it is preferable to provide an intermediate layer to ensure adhesion and injection blocking effect. 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 the purpose of adjusting compatibility with the manufacturing process before forming the photosensitive layer, such as a pre-treatment method for a conductive substrate, an intermediate layer may be provided as a further form.

FIG. 6 shows, as a further embodiment, an intermediate layer (5), a charge transport layer (2) and a charge generation FJ (
3) and a surface protective layer (4) are laminated in the first order. 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 accordingly, providing the intermediate layer and the surface protective layer in the configurations shown in FIGS. 2 and 3 can be a further 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 a gas phase by discharge decomposition under reduced pressure, and diffuses active neutral species or charged species contained in the generated plasma atmosphere onto the substrate, using electric force or magnetic force. It is preferable that the polymer be generated by a so-called plasma polymerization reaction, which is induced by 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 tank has the first to sixth control valves (707
) ~ (712) and the first to sixth flow rate controllers (713) ~
(718). (719) to (72) in the figure
1) are first to third containers containing raw material compounds that are in a liquid or solid state at room temperature, and each container is heated by the first to third temperature regulators (722) to (724) for vaporization. Further, each container has seventh to ninth control valves (725) to (727) and seventh to ninth flow rate controllers (725) to (727).
728) to (730). These gases are mixed in a mixer (731) and then sent into a reaction chamber (733) via a main pipe (732). The intermediate piping can be heated by an appropriately placed piping heater (734) so that the gas, which is the vaporized raw material compound that is in a liquid phase or the same phase at room temperature, does not condense on the way. 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 an electrode heater (737). A high frequency power supply (739) and a low frequency power matching box (74) are connected to the power applying electrode (736) via a matching box for high frequency power (738).
A low frequency power source (741) is connected through a low-frequency power source (741) through a low-pass filter (742), and a DC power source (743) is connected through a low-pass filter (742), and power with different frequencies can be applied by a connection selection switch (744). The pressure inside the reaction chamber (733) can be adjusted by a pressure control valve (745), and the pressure inside the reaction chamber (733) can be reduced through an exhaust system selection valve (746), a diffusion pump (747), and an oil rotary valve. Pump (74
8), or cooling exclusion device (749), mechanical booster pump (750), oil rotary pump (748)
This is done by The exhaust gas is further rendered safe and harmless by an appropriate exclusion device (753) before being exhausted into the atmosphere. These exhaust system piping can also be heated by appropriately placed piping heaters (734) to prevent the vaporized gas of the raw material compound, which is in a liquid or solid phase state at room temperature, from condensing on the way. ing. reaction chamber (
733) can also be heated by the reaction chamber heater (751) for the same reason, and a conductive substrate (752) is installed on the electrode arranged inside. In Figure 7, the conductive substrate (
752) are fixedly disposed on the ground electrode (735), but may be fixedly disposed on the power application electrode (736), or may be disposed roughly on both sides.

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 appended numbers can be understood by replacing the 700s with 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) There is also a cylindrical power application electrode (
836) is arranged, and an electrode heater (837) is arranged outside. 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 10-6 Torr, and the degree of vacuum is confirmed 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 rate using the first to ninth flow rate controllers, and the inside of the reaction chamber is kept constant using the pressure control valve. Maintain a reduced pressure. 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 starts between the two electrodes, and over time a solid phase film is formed on the substrate. The a-Si film or the a-C film can be formed arbitrarily by changing the source 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 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, in a desired photoreceptor configuration,
If a charge generation layer or an overcoat layer is required, the photoreceptor according to the present invention can be fabricated by using the present device as is, or by breaking the vacuum and transferring it to another device to provide these layers. get.

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

As an example, 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. Fourth control valve (7
07, 708, 709, and 710), hydrogen gas from the first tank (701), acetylene gas from the second tank (702), oxygen gas from the third tank (703), and fourth tank (704). The first, second, third, and fourth flow rate controllers (713, 714, 715, and 71
6) Allowed to flow into the interior. Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 180 seconds, the acetylene gas flow rate to 40 seconds, and the oxygen gas flow rate to 4 seconds.
, and the flow rate of carbon tetrafluoride gas is set to 10105e, and the main pipe (7
32) into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 2.0T.
The pressure control valve (745) was adjusted so that the

On the other hand, as a conductive substrate (752), 50 fir x 50
Using an aluminum substrate with a thickness of 3 mm, heat it to 250°C in advance.
After heating to , and with the gas flow and pressure stable,
Turn on the high frequency power supply (739) that has been connected in advance using the connection selection switch (744), and connect the power application electrode (736).
) at a frequency of 13.56 MHz to carry out a plasma polymerization reaction for about 3 hours to form a 15 μm thick a-C film as a charge transport layer on the 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.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 34 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, fluorine atoms, was 2.0 at % based on the total constituent atoms, and the amount of oxygen atoms was 1.1 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) 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 controllers (713, 714, and 7
18) It was allowed to flow into the interior. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec, the germane gas flow rate to 0.6 sec, and the silane gas flow rate to 10100 sec.
5e and flowed into the reaction chamber (733). After each flow rate stabilizes, the pressure in the reaction chamber (733) becomes 0.
．． The pressure regulating valve (745) was adjusted to 8 Torr. On the other hand, a conductive substrate (7
52) is heated to 250°C, and when the gas flow rate and pressure are stable, a frequency of 1 is applied from the high frequency power supply (739).
35W to the power application electrode (736) under 3.56MHz
Att power was applied to generate glow discharge. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

When the obtained a-Si film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho) and Auger analysis, it was found that the hydrogen atoms contained were 2% of all constituent atoms.
The content of germanium atoms was 0 at%, and the content of germanium atoms was 1 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 -610V (+770V).In other words, since the total photoreceptor film thickness is 15°3μm, the charging ability per μm is 40V. ■/μm (50V/μm), which is extremely high.
From this, it was understood that it had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 17 seconds (approximately 25 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 brightly attenuate the surface potential to 20% of the highest charging potential, and the amount of light required was 3.0 lux · seconds (4.0 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.

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. Control valve (707
, 708, 709, and 710), hydrogen gas from the first tank (701), ethylene gas from the second tank (702), oxygen gas from the third tank (703), and hydrogen gas from the fourth tank (704). Carbon chloride gas was supplied to the first, second, third, and fourth stations under an output pressure of 1゜0Kg/cm2, respectively.
It was made to flow into the flow rate controllers (713, 714, 715, and 716). Then adjust the scale of each flow controller,
The flow rate of hydrogen gas was set to 60 seconds, the flow rate of ethylene gas was set to 60 seconds, the flow rate of oxygen gas was 4 sccms, and the flow rate of carbon tetrachloride gas was set to 20 seconds. The liquid then flowed into the reaction chamber (733). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 2.0 Torr.

On the other hand, the conductive substrate (752) has a height of 50 x width of 50
× Using an aluminum substrate with a thickness of 3 mm, heat the temperature at 230°C in advance
After heating to , and with the gas flow and pressure stable,
Turn on the high frequency power supply (739) that has been connected in advance using the connection selection switch (744), and connect the power application electrode (736).
) was applied at a frequency of 13.56 MHz with a power of 200 Wa 11 to carry out an open planar plasma polymerization reaction for about 3 hours, and a 15 μm thick a-C film was formed as a charge transport layer on the 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.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 42 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, chlorine atoms, was 4.9 at% based on the total constituent atoms, and the amount of oxygen atoms was roughly 1.0 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) and the 6th iJil1 section valve (71
2), hydrogen gas from the first tank (701), germane gas from the second tank (702), and silane gas from the sixth tank (706) are supplied to the first and second tanks under an output pressure of IKg/cm2. , and the sixth flow rate controller (713, 714
, and 718). Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 seconds, the germane gas flow rate to 2 seconds, and the silane gas flow rate to 101 seconds.
005e and flowed 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 0.8 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 250°C, and is heated at a frequency of 13.56 MHz from a high frequency power source (739) while the gas flow rate and pressure are stable. A power of 35 Watts was applied to the power application electrode (736) to generate glow discharge.

This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

When the obtained a-3iFi was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho) and Auger analysis, it was found that the hydrogen atoms contained were 20 atomic% and the germanium atoms contained were 3 atoms based on the total constituent atoms. %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 at the time of positive charging are shown in parentheses, and the highest charging potential is -480V (+610V), 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 (40 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 15 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 brightly attenuate the surface potential to 20% of the highest charging potential.The amount of light required was 1.2 lux seconds (1.6 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 charging potential using semiconductor laser light (emission wavelength: 780 nm)? ,8e
rg/cm2 (9.4 erg/cm2), and from this it was understood that it had sufficient long wavelength light sensitivity 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. Setben (70
7, 709, and 710) and release the first tank (70
1) Hydrogen gas from the third tank (703), oxygen gas from the fourth tank (704), and tetrafluorine gas from the fourth tank (704) were supplied to the first, third, and third tanks at an output pressure of 1.0 Kg/cm2, respectively. 4
It was made to flow into the flow controllers (713, 715, and 716).

At the same time, styrene gas is poured into the first container (719).
Tune! (722) The seventh flow controller (at a temperature of 35°C)
728). Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 60 sec, the styrene gas flow rate to 30 sec, and the oxygen gas flow rate to 8 sec.
Set the flow rate of c mz and carbon tetrafluoride gas to 30 seconds, and mix in the middle 8 (731)! Intercession, Lord! (732) into the reaction chamber (733). After each flow rate stabilizes, the pressure control valve (745) is opened so that the pressure in the reaction chamber (733) becomes 2°0 Torr.
adjusted. On the other hand, as the conductive substrate (752), an aluminum substrate of 50×50×3 mm in thickness is used, heated to 180°C in advance, and connected with the connection selection switch (744) in a state where the gas flow rate and pressure are stable. Turn on the low frequency power supply (741) that has been prepared, and apply 200 Watt power to the power application electrode (736) at frequency 12.
Plasma polymerization reaction was performed for about 45 minutes by applying 0 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.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 48 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, that is, fluorine atoms, was 6.1 at% based on the total constituent atoms, and the amount of oxygen atoms was 2.3 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) 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 controllers (713, 714, and 7
18) It was allowed to flow into the interior. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200sec, the germane gas flow rate to 6sccm1, and the silane gas flow rate to 101005e.
was set to flow into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 0.9
The pressure control valve (745) was adjusted so that the pressure was Torr. On the other hand, a conductive substrate (75
2) is heated to 250℃, and with the gas flow rate and pressure stable, a frequency of 13 is applied from the high frequency power supply (739).
．． 40W to power application electrode (736) under 56MHz
A glow discharge was generated by applying a power of tt.

This discharge was performed for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

When the obtained a-Si film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho) and Auger analysis, the number of hydrogen atoms that could be contained was 2 for all constituent atoms.
The content of germanium atoms was 0 atom %, and the content of germanium atoms was 10 atom %.

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 -460V (+560V), that is,
Since the total photoreceptor film thickness was 15.3 .mu.m, the charging ability per 1 .mu.m was extremely high at 30 V/.mu.m (36 V/.mu.m) (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 11 seconds (approximately 14 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 using white light to a surface potential of 20% of the highest charging potential, and the amount of light required was 1.1 lux · seconds (1.5 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 brightness to a surface potential of 20% of the highest charging potential using semiconductor laser light (emission wavelength 780 nm)? , O
erg/am2 (9, lerg/cm2), and from this it was understood that it had sufficient long wavelength light sensitivity 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.

Example 4 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. Fourth control valve (7
07, 708, 709, and 710), hydrogen gas from the first tank (701), butadiene gas from the second tank (702), carbon dioxide gas from the third tank (703), and fourth tank (704). Carbon tetrafluoride gas was then flowed into the first, second, third, and fourth flow rate controllers (713, 714, 715, and 716) under an output pressure of 1.0 Kg/cm2, respectively. Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 60scam, the butadiene gas flow rate to 60sec, and the carbon oxide gas flow rate to 1.
2 sec, and the flow rate of carbon tetrafluoride gas is 160 sec.
m, 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 in the reaction chamber (733) was 1.6 Torr. On the other hand, as the conductive substrate (752), fir 5
Using an aluminum substrate of 0 x width 50 x thickness 3 mm, it was preheated to 120°C, and with the gas flow rate and pressure stable, it was connected to the low frequency power source (741) using the connection selection switch (744). ) and apply 130W of power to the power application electrode (736) at a frequency of 600K.
Plasma polymerization reaction was carried out under Hz for about 1.5 hours to form a 15 μm thick a-C film as a charge transport layer on the 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 above, the amount of hydrogen atoms contained was 51 at% based on the total amount of carbon atoms and hydrogen atoms, and according to Auger analysis, the amount of hydrogen atoms contained was 51 atomic %. The amount of halogen atoms, ie, fluorine atoms, was 18.0 at% based on all the constituent atoms, and the amount of oxygen atoms was 2.0 at% based on all the 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) 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/am2.
, second, and sixth flow rate controllers (713, 714, and 7
18) It was allowed to flow into the interior. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec, germane gas flow rate to 205 CCrrh and silane gas flow rate to 1010 sec.
05e to flow into the reaction chamber (733). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 1.0 Torr. On the other hand, a conductive substrate (
752) is heated to 250°C, and with the gas flow rate and pressure stable, a high frequency power source (739) applies power to the electrode (736) at a frequency of 13° and 56 MHz.
Watt's electric power was applied to generate glow discharge. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

Next, the obtained a-Si film was subjected to ○NH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho) and Auger analysis, and it was found that the hydrogen atoms contained were 2% of the total constituent atoms.
The content of germanium atoms was 0 atom %, and the content of germanium atoms was 30 atom %.

Characteristics: When the obtained photosensitive method was used in a conventional Carlson process with both negative and positive charging, the following properties were obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -200V (+210V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was as high as 13 V/.mu.m (14 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 is approximately 3 seconds (approximately 2.5 seconds).
From this, it was understood that the material has charge retention performance that poses no problem in practical use. Furthermore, after initial charging to the highest charging potential, white light was used to attenuate the surface potential to 20% of the highest charging potential, and the amount of light required was 5.
2 lux·sec (4.4 lux·sec), and from this it was understood that it had sufficient photosensitivity performance.

From the above, it can be concluded 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. Control valve (707
, 708, 709, and 710), hydrogen gas from the first tank (701), butadiene gas from the second tank (702), oxygen gas from the third tank (703), and hydrogen gas from the fourth tank (704). First, second, third, and fourth flow rate controllers (713, 714, 715, and 716) each supplying fluorocarbon gas under an output pressure of 1.0 Kg/am2.
It flowed inside. Then, adjust the scales of each flow rate ephemeral and set the flow rate of hydrogen gas to 180 seconds, the flow rate of butadiene gas to 40 seconds, the flow rate of oxygen gas to 4 seconds, and the flow rate of carbon tetrafluoride gas to 10105e. (731), main pipe (732)
) into the reaction chamber (733). After each flow rate stabilized, the pressure inside the reaction chamber (733) reached 2.0 Torr.
The pressure regulating valve (745) was adjusted so that the temperature was r. On the other hand, as the conductive substrate (752), use an aluminum substrate of M50 x width 50 x thickness 3 mm, heat it to 180°C in advance, and when the gas flow rate and pressure are stable, connect the connection selection switch (744) in advance. The low-frequency power source (741) connected to the conductive substrate (752) is turned on, and 200 Watt power is applied to the power application electrode (736) at a frequency of 600 KHz to perform a plasma polymerization reaction for about 30 minutes. 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.

When organic elemental analysis was performed on the a-C film obtained as above, the amount of hydrogen atoms contained was 40 at% based on the total amount of carbon atoms and hydrogen atoms, and according to Auger analysis, the amount of hydrogen atoms contained was The amount of halogen atoms, ie, fluorine atoms, was 4.1 atomic % based on all the constituent atoms, and the amount of oxygen atoms was 1.8 atomic % based on all the constituent atoms.

Charge generation layer forming step: Next, some of the tanks were replaced, and the first control valve (7o7)
The second control valve (708), the third control valve (7o9), and the sixth control valve (712) are opened, 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 IKg/c.
The first, second, third, and sixth flow controllers (7
13,714,715, and 718).

Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200.
The flow rate of the silane tetrafluoride gas was set to 50 sec, the flow rate of the germane gas was set to 6 s CCm, and the flow rate of the silane gas was set to 50 sec cm, and these were flowed into the reaction chamber (733). After each flow rate stabilized, the reaction chamber (73
3) The pressure regulating valve (745) was adjusted so that the pressure inside was 0.9 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 230°C.
With the gas flow rate and pressure stable, turn on the high frequency power supply (73
9), the power application electrode (
736) to generate a glow discharge. This discharge was carried out for 5 minutes, and a thickness of 0.3 μm was formed.
A charge generation layer was obtained.

When the obtained a-3i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho) and Auger analysis, it was found that the amount of hydrogen atoms contained was 1 for all constituent atoms.
8 atom%, fluorine atom 5 atom%, germanium atom 1
It was 1 atomic %.

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 -500V (+640V), 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 33 V/.mu.m (42 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 13 seconds (approximately 16 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, and the amount of light required was 2. flux-second (3.6 lux-second), 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.

[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 halogen atoms; 1. A photoreceptor comprising a fluorinated or fluorinated amorphous silicon germanium film.