JPS6382443A - Photosensitive body - Google Patents

Abstract

PURPOSE:To form a photosensitive layer which has excellent photosensitive characteristics and is extremely thin in film thickness by forming an electric charge transfer layer of a hydrogenated amorphous carbon film contg. oxygen and halogen atoms and an electric charge generating layer of a hydrogenated or fluorinated amorphous silicon film contg. oxygen and at least either of phosphorus or boron atoms, respectively. CONSTITUTION:The charge transfer layer 2 of a function sepn. type photosensitive body having the charge transfer layer 2 and the charge generating layer 3 is formed of the hydrogenated amorphous carbon a-C film which is formed by glow discharge and contains the oxygen atoms and halogen atoms and the charge generating layer 3 is formed of the hydrogenated or fluorinated amorphous silicon a-Si film which contains at least either of the phosphorus atoms or boron atoms and contains the oxygen atoms. The content of the oxygen in the a-Ci film is specified to <=7atom% and the content of the halogens to 0.1-25%. The content of the oxygen in the a-Si film is specified to 0.001-1% and the content of the phosphorus or boron to <=20,000ppm. The charge transfer layer 2 is thereby improved in transferability, electric chargeability, durability and translucency, and the charge generating layer 3 is provided with the excellent photoconductivity of visible light and wavelength light near laser light and is extremely reduced in the film thickness.

Description

[Detailed description of the invention] Cliff! 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 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, conventionally used electrophotographic photoreceptor materials each have their own 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 overcome these 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 speaking, amorphous silicon has low charging performance due to its low dielectric constant, and it is necessary to increase the thickness of the film in order to charge it to a predetermined surface potential in a copying machine. You have to accumulate 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, published in 1973 by
nal of Applied P.

lymer 5science), Volume 17, pages 885 to 892, it was also reported by the same author that all organic compounds can be produced from gases, in the 1979 American Chemical Society (Amer 1c).
Plasma Volumarization (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 requiring insulating properties, that is, they are considered to be absolute films with a specific resistance of about <1018 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 thereon. ing. Japanese Patent Application Publication No. 5
Publication No. 9-38753 discloses that a plasma polymerized film with a high resistance of 1013 to 1015 Ωcm, which is generated from a mixed gas of oxygen, nitrogen, and hydrocarbon, is provided on a substrate as a blocking layer and an adhesive layer by 10 to 100 people. A photoreceptor is disclosed that includes an amorphous silicon layer. 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 a film thickness of 2 μm or less is preferable from the viewpoint 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-Si
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 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 has been disclosed in which an amorphous carbon or hard carbon film with a thickness of about 5 μm is used as a surface protective layer, and it is said that if the film thickness exceeds 5 μm, 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
3579, 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.

As mentioned above, plasma organic polymer films conventionally used in electrophotographic photoreceptors have been used as so-called undercoat layers or overcoat layers, but they have a carrier transport function. It is a film that does not require an organic polymer film, and is used based on the judgment that the organic polymer film is insulating. Therefore, it is only used as a very thin film with a thickness of about 5 um at most, and carriers either pass through the film by tunneling effect, or if tunneling effect cannot be expected, there is virtually no problem with the generation of residual potential. 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 discovered that hydrogenated amorphous carbon films, which were originally thought to be insulating, contained oxygen atoms and halogen atoms. In some cases, when laminated with a hydrogenated or fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms and oxygen atoms, it has charge transport properties and is easily suitable for electrophotography. It was discovered that the characteristics began to be shown. Although the theoretical interpretation has many unclear points even for the present inventors, it is not possible to discuss it in detail. An electron in a stable energy state, e.g. π
The band structure formed by electrons, unpaired electrons, residual free radicals, etc. is a band formed by a hydrogenated or fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms as well as oxygen atoms. It occurs in a hydrogenated or fluorinated amorphous silicon film that contains at least one of phosphorus atoms and boron atoms as well as oxygen atoms because it has similar energy levels in the structure and conduction band or valence band. The carriers are easily injected into the hydrogenated amorphous carbon film containing oxygen atoms and halogen atoms, and furthermore, these carriers are injected into oxygen atoms and halogen atoms by the action of the electrons in the relatively unstable energy state mentioned above. It is presumed that this is because the hydrogenated amorphous carbon film can run suitably through the hydrogenated amorphous carbon film containing the 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 A hydrogenated amorphous carbon film containing atoms and halogen atoms is used as a charge transport layer, and hydrogenated or fluorine containing at least one of phosphorus atoms and boron atoms as well as oxygen atoms. An object of the present invention is to provide a photoreceptor using a thin film of amorphous silicon as a charge generation layer.

To solve this problem, the present invention provides a functionally separated photoreceptor having a charge generation layer and a charge transport layer, in which the charge transport layer contains at least oxygen atoms and halogen atoms generated from a plasma polymerization reaction. hydrogenated or fluorinated amorphous silicon in which the charge generation layer contains at least one of phosphorus atoms and boron atoms and also contains oxygen atoms; The present invention relates to a photoreceptor characterized in that it is a film (hereinafter, the charge transport layer according to the present invention will be referred to as an a-C film and the charge generation layer will be 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 requires only 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 produced by glow discharge as a charge transport layer, and a hydrogenated amorphous carbon film containing at least oxygen atoms and halogen atoms produced 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 film containing at least one of atoms and boron atoms and oxygen atoms. 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 good 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 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 a state of the hydrocarbon does not necessarily have to be in the gas phase at normal temperature and pressure, but can be melted by heating or reduced pressure, etc.
As long as it can be vaporized through evaporation, sublimation, etc., either liquid phase or solid phase can be used.

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, tetracane, undecane, tridecane, 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, neo Hexane, 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-trimethylpentane, 2,3°3-trimethylpentane, 2,3,4-trimethylpentane, isonanone, etc. are used. Examples of unsaturated hydrocarbons include ethylene, propylene, imbutylene, 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, pentagene, hexadiene, cyclopentadiene, and triolefins such as ocimene, alloocimene, myrcene, hexatritamine, and the like; , acetylene, butadiyne, 1゜3-pentadiyne, 2.4-hexadiyne, methylacetylene, 1-butyne, 2-butyne, 1-pentyne, l-hexyne, l-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, hemimelithene, pseudocumene, mesitylene, prenitene, isodurene, durene,
Pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, piphenyl, 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 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 a combination of these methods can reduce the hydrogen content. It has the effect of lowering the amount.

The thickness of the a-C film as the charge transport layer in the present invention is 5 to 5
0 μm s, especially 7 to 20 μm is suitable, and 5 μm
If it is thinner than m, the charged potential will be low, making it impossible to obtain a sufficient density of the copied image. 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, microwave, etc. is the most preferable, but it may also be formed through an ionic state generated by ionization vapor deposition, ion beam vapor deposition, etc., or a neutral state generated by vacuum vapor deposition, sputtering, etc. It may be formed from particles or a combination thereof.

In the present invention, in addition to hydrocarbons, oxygen compounds are 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 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 oxygen, ozone, water vapor, -carbon oxide, carbon dioxide, carbon suboxide, and other inorganic compounds, hydroxyl groups (-OH),
Aldehyde group (-COH), acyl group (RCO-, -
Organic compounds having functional groups or bonds such as CRO), ketone groups (>Co), ether bonds (-〇-), ester bonds (-Coo-), and oxygen-containing heterocycles are used. Examples of organic compounds having a hydroxyl group include:
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, palmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, toluic acid, salicylic acid, and cinnamon. 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, methyl heptenone, cyclobutanone, cyclopentanone, cyclohexanone, acetophenone, Propiophenone, butyrophenone, valerophenone, 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, and ethyl amyl ether. , vinyl ether, allyl ether, methyl vinyl ether, methyl furyl ether, ethyl vinyl ether, ethyl furyl ether,
Anisole, phenethole, phenyl ether, benzyl ether, phenylbenzyl ether, naphthyl ether, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydrobilane, dioxane, and the like are used. Examples of organic compounds having an ester bond include methyl formate, ethyl formate, propyl formate, butyl formate, amyl formate, methyl #acid, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl propionate, and ethyl propionate. , propionate a
Byl, 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, benzoate Ethyl acid, methyl cinnamate, ethyl cinnamate, propyl cinnamate, methyl salicylate, ethyl salicylate, propyl salicylate, butyl salicylate, amyl salicylate, methyl anthranilate, ethyl anthranilate, butyl anthranilate, amyl anthranilate, phthalate Methyl acid, ethyl phthalate, butyl phthalate, etc. are used. Examples of heterocyclic compounds containing oxygen include furan, oxazole, furazane, biran, oxazine, morpholine, benzofuran, banzoxazole, 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 less than 7.0 at%, the oxygen atoms, which had guaranteed good transport properties when added in small amounts, conversely exhibit the effect of lowering the resistance of the film, causing a decrease in charging ability. cause a decline. 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 to the a-C film according to the present invention, and conversely, if the amount of oxygen compounds introduced is decreased, the amount of oxygen atoms added to 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-CM. 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,
Inorganic compounds such as chlorine, bromine, iodine, hydrogen fluoride, chlorine fluoride, bromine fluoride, iodine fluoride, hydrogen chloride, bromine chloride, iodine chloride, hydrogen bromide, iodine bromide, hydrogen iodide, etc., and halogenated Organic compounds such as alkyl, halogenated aryl, halogenated styrene, halogenated polymethylene, and heroform are used. Examples of alkyl halides include methyl fluoride, methyl chloride, methyl bromide, methyl iodide, ethyl fluoride, ethyl chloride, ethyl bromide, ethyl iodide, propyl fluoride, propyl chloride, propyl bromide, and Propyl chloride, butyl fluoride, butyl chloride, butyl bromide, butyl iodide, amyl fluoride, amyl chloride, amyl bromide, amyl iodide, hexyl fluoride, hexyl chloride, hexyl bromide, hexyl iodide, fluoride Hebutyl, heptyl 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, methylene 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. Examples of heloform include fluoroform, chloroform, bromoform, iodoform, and the like.

In the present invention, the amount of halogen atoms 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 at%, the halogen atoms, which had guaranteed suitable charge transport properties and prevention of residual potential generation when added in an appropriate amount, will conversely cause a decrease in charging ability, and even worse over time. It has the effect of lowering the dark resistance of the cell, 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 a-CF2 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 a-CF2 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-8iPA. Furthermore, phosphine gas, diborane gas, or the like is used as a raw material gas for incorporating phosphorus atoms or boron atoms as chemical modifiers into the film. In general, an oxygen compound gas such as oxygen gas, nitrous oxide gas, ozone gas, or -carbon oxide gas is used as a raw material gas for containing oxygen atoms as a chemical modifier in the film.

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.

In the present invention, the amount of oxygen atoms contained as a chemical modifier is 0.001 to 1 atomic% based on the total constituent atoms.
It is. Here, the content of oxygen atoms in the film can be determined by a conventional method of elemental analysis, such as Auger analysis or IMA analysis. When the content of oxygen atoms in the film is lower than 0.001 at%, the electric resistance value of the a-Si film becomes low, making it difficult for a-3iFJ to be subjected to electric fields due to corona charging, etc., and photoexcited carriers are not necessarily Efficiency <a-C is no longer injected into the film, resulting in a decrease in sensitivity. Furthermore, the charging ability is also reduced. If the content of oxygen atoms in the film is higher than 1 atomic %, the electrical resistance of a-Siv becomes too high, which reduces the generation efficiency and mobile speed of photoexcited carriers, leading to a decrease in sensitivity. invite Therefore, the range of the amount of oxygen atoms added in the present invention is important.

The amount of hydrogen atoms or fluorine atoms contained in the a-3i 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 is 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-3i 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,
In general, 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-5i 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 oxygen atoms, phosphorus atoms, or boron atoms contained as chemical modifiers is mainly determined by the amount of oxygen compound gas, phosphine gas, or diborane gas introduced into the reaction chamber in which the plasma reaction is performed. It is possible to change the printing area by increasing or decreasing the amount of introduced. By increasing the amount of oxygen compound gas, phosphine gas, or diborane gas introduced, oxygen atoms, phosphorus atoms,
Alternatively, it is possible to increase the amount of boron atoms added,
On the other hand, if the amount of oxygen compound gas, filamentous gas, or diborane gas introduced is reduced, the amount of oxygen atoms, phosphorus atoms, or boron atoms added to the a-Si film according to the present invention can be reduced. Is possible.

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 form thereof, a structure in which a charge transport layer (2) and a charge generation M (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 Figure 2, electrons generated in the charge generation layer (3) travel towards the surface of the photoreceptor in the charge transport layer (2), and in Figure 3, electrons are generated in the conductive substrate (1). Holes generated in the layer (3) travel toward the conductive substrate (1) through the charge transport layer (2) on the conductive substrate side, and at the same time travel through the charge generation layer (2) toward the conductive substrate (1).
The electrons generated in step 3) travel toward the surface of the photoreceptor through the charge transport layer (2) on the front side, forming an electrostatic latent image guaranteed to have suitable brightness attenuation. 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), 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-Si film with poor moisture resistance, in many cases it is preferable to provide a surface protective layer in order 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 a further embodiment.

FIG. 5 shows an intermediate layer (5), a charge generation layer (3), and a charge transport N (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 surface protection Pi (4) is 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 installing the intermediate layer and the surface protective layer is the same as described above, so in the configurations shown in FIGS.
Providing layers can also 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 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 material be generated through 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 photoreceptor manufacturing apparatus according to the present invention.
701) to (706) are the first to sixth tanks in which raw material compounds and carrier gas which are in a gas phase at room temperature are sealed, and each tank is connected to the first to sixth FI 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. Roughly 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 pipes along the way can be heated by appropriately placed pipe heaters (734) so that the gas, which is the vaporized raw material compound that is in a liquid or solid state 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). The power application electrode (736) is connected to a high frequency power source (739) and a matching box for low frequency power (74) via a matching box for frequency power (738).
A low frequency power source (741) is connected through a low-frequency power source (741) 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 (748
), 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 is started between the two electrodes, and a solid phase film is formed on the substrate over time. The a-3i film or the a-C film 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 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 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. Fourth control valve (7
07, 708, 709, and 71O), 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).
) was applied with a power of 200 Watts at a frequency of 13.56 MHz to carry out a plasma polymerization reaction for about 3 hours, thereby forming an a-C film with a thickness of 15 μm 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 roughly 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 fifth control valve (711) and the sixth control valve (712) are released, hydrogen gas is supplied from the first tank (701), nitrous oxide gas is supplied from the S tank (705), and the sixth tank (70
6) into the first, fifth and sixth streams'! under an output pressure of IKg/cm2. #, control tM device (713, 71
7, and 718). At the same time, the fourth control valve (710) is opened, and phosphine gas diluted to 10 ppm 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 controller to set the hydrogen gas flow rate to 200 sec and the nitrous oxide gas flow rate to 1 sec.
At 0105e, the flow rate of silane gas was set to 10105e, and the flow rate of phosphine gas diluted to 1100 pp with 2003 CCm% hydrogen gas was flowed into the reaction chamber (733). After each flow rate is stabilized, the pressure regulating valve (74) is adjusted so that the pressure in the reaction chamber (733) becomes 0.8 Torr.
5) was adjusted. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 230°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. Power application electrode (736
) was applied with a power of 35 Watts 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.

The obtained a-3i film was subjected to ○NH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and IM.
Analysis A revealed that the hydrogen atoms contained were 22 at %, the phosphorus atoms were 10 at ppmz, and the oxygen atoms were 1.0 at % based on the total constituent atoms.

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 M potential is -790V (+950V), 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 52 .mu./.mu.m (62 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 22 seconds (approximately 28
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 4.0 lux·sec (12.9 lux・Seconds), and from this it was concluded 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. and the fourth control valve (7
07, 708, 709, and 71Q), hydrogen gas from the first tank (701), ethylene gas from the second tank (702), oxygen gas from the third tank (703), and oxygen gas from the fourth tank (704). The first, second, third, and fourth flow rate controllers (713, 714, 715, and 716) each supply carbon tetrachloride gas under an output pressure of 1°0 Kg/am2.
It flowed inside. Then, adjust the scales of each flow rate controller to set the flow rate of hydrogen gas to 60 seconds, the flow rate of hydrogen gas to 60 seconds, the flow rate of oxygen gas to 4 seconds, and the flow rate of carbon tetrachloride gas to 20 seconds. It flowed into the reaction chamber (733) from the main pipe (732) via the 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 2.0 Torr.

On the other hand, as the conductive substrate (752),! 50X horizontal 50
Using an aluminum substrate with a thickness of 3 mm, heat it to 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).
) with a power of 200 W all at a frequency of 13.56 MH
A plasma polymerization reaction was carried out for about 3 hours by applying voltage under z, 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 were replaced, and the first control valve (7o7)
The fifth control valve (711) and the sixth control valve (712) are released, hydrogen gas is supplied from the first tank (701), nitrous oxide gas is supplied from the fifth tank (705), and the sixth tank (70
6) was flowed into the first, fifth, and sixth flow controllers (713, 717, and 718) under an output pressure of IKg/cm2. At the same time, the fourth control valve (710
) and 11 with hydrogen gas from the 4th tank (704).
Diborane gas diluted to 00pp is output at an output pressure of 1.5K.
g/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 seconds and the flow rate of nitrous oxide gas to 0.01 seconds.
ecm, the flow rate of silane gas is 1001005e the flow rate of diborane gas diluted to 1100pp with hydrogen gas is 10
105e, and 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, the conductive substrate (752) on which the a-C film is formed is heated to 250°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.

The obtained a-Si 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 22 atomic% and the boron atoms were 10 atomic ppm based on the total constituent atoms.
, oxygen atoms were 0.001 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 -600V (+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 39 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 the surface potential to darken from Vmax to 90% of Vmax in the dark is approximately 15 seconds (approximately 1
5 seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, bright decay was performed using white light to a surface potential of 20% of the highest charging potential.・seconds), and from this it was understood that it had sufficient photosensitivity 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 a commonly used curling 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. Valve (707,
709 and 710), and the first tank (701)
Hydrogen gas, oxygen gas from the third tank (703), and carbon tetrafluoride gas from the fourth tank (704) are controlled at the first, third, and fourth flow rates under an output pressure of 1.0 Kg/cm2, respectively. into the vessels (713, 715, and 716).

At the same time, styrene gas is supplied from the first container (719) to the first temperature controller (722) at a temperature of 35°C and to the seventh flow rate $1S unit (
728). Then adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 60 sec and the styrene gas flow rate to 30 sccrr+.

Set the flow rate of oxygen gas to 8 sccrrb and the flow rate of carbon tetrafluoride gas to 30 sccm, and mix in the middle!
(731) from the main pipe (732) to the reaction chamber (73).
3) It flowed into the interior. 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, a conductive substrate (75
For 2), use an aluminum substrate measuring 50 mm long x 50 mm wide x 3 mm thick, heat it to 180 degrees Celsius in advance, and with the gas flow rate and pressure stable, press the connection selection switch (
The low frequency power source (741) connected to the conductive substrate (744) is turned on, and 200 Watts of power is applied to the power application electrode (736) at a frequency of 120 KHz to perform a plasma polymerization reaction for about 45 minutes. 752), a 15 μm thick a-C film was formed thereon as a charge transport layer. After film formation is complete, stop applying power, close the control valve, and close 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, ie, fluorine atoms, was 6.1 atomic % based on the total constituent atoms, and the amount of oxygen atoms was 2.3 atomic % based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
5th FIff15 valve (711) and 6th control valve (71
2), hydrogen gas is supplied from the first tank (701), oxygen gas is supplied from the fifth tank (705), and sixth tank (705) is released.
06) was flowed into the first, fifth, and sixth flow controllers (713, 717, and 718) under an output pressure of IKg/cm2. At the same time, the fourth boiled valve (71
0) and 1 with hydrogen gas from the fourth tank (704).
Diborane gas diluted to 100 pp is heated to an output pressure of 1°5.
It was allowed to flow into the fourth flow controller (716) under Kg/cm2. Adjust the scale of each flow rate controller to FA to set the hydrogen gas flow rate to 200 sec and the oxygen gas flow rate to 0.5 sec.
The flow rate of ms silane gas is 11005ca, and the flow rate of hydrogen gas is 1
The flow rate of diborane gas diluted to 100pp is 1010
5e and flowed into the reaction chamber (733). After each flow rate stabilizes, the pressure in the reaction chamber (733) becomes 0.
．． The pressure control valve (745) was adjusted to 9 Torr. On the other hand, a conductive substrate (7
52) is heated to 230°C, and when the gas flow rate and pressure are stable, the high frequency power supply (739) is heated to a frequency of 1.
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-3i film was subjected to ○NH analysis in metal (Itaba Seisakusho tAEMGA-1300), Auger analysis, and IMA analysis, it was found that the hydrogen atoms contained were 20 atomic% based on the total constituent atoms. Boron atom has 12 atom pI
) rrh oxygen atoms were 0.1 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 -740V (+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 48 .mu./.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 90% of Vmax in the dark was approximately 17 seconds (approximately 19 seconds).
seconds), and from this we can understand that it has sufficient charge retention performance. Furthermore, 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 1. flux-second (1.4 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.

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. 4 control valve (707
, 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 carbon dioxide gas from the fourth tank (704). Carbon tetrafluoride gas was supplied to the first, second, third, and
and fourth flow rate controller (713, 714, 715, and 7
16) It flowed inside. Then, adjust the scales of each flow rate controller to set the flow rate of hydrogen gas to 60 sccm, the flow rate of butadiene gas to 60 seconds, and the flow rate of carbon dioxide gas to 12 seconds.
secm, and the flow rate of carbon tetrafluoride gas is 160 sec
The mixture was set so as to flow 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 a conductive substrate (752),
Using an aluminum substrate of 0x width 50x thickness 3mm, heat it in advance to 120°C, and with the gas flow rate and pressure stable, connect the low frequency power supply (741) with the connection selection switch (744) in advance. ) and apply 130W of power to the power application electrode (736) at a frequency of 700K.
Plasma polymerization reaction was carried out for about 1.5 hours under application of Hz, and an a-C film having a thickness of 15 μm 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 51 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, that is, fluorine atoms, is 18. Roughly speaking, the amount of oxygen atoms was 2.0 atom % based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks were replaced, and the first control valve (7o7)
The fifth control valve (711) and the sixth control valve (712) are released, hydrogen gas is supplied from the first tank (701), nitrous oxide gas is supplied from the fifth tank (705), and the sixth tank (70
6) was flowed into the first, fifth, and sixth flow controllers (713, 717, and 718) under an output pressure of IKg/am2. At the same time, the fourth control valve (710
) and 11 with hydrogen gas from the 4th tank (704).
Diborane gas diluted to 00pp is output at an output pressure of 1.5K.
It was made to flow into the fourth flow restrictor (716) under 1 g/cm2. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec cm and the nitrous oxide gas flow rate to 3 sec.
m, the flow rate of silane gas is 101005e, and the flow rate of hydrogen gas is 1
The flow rate of diborane gas diluted to 00 ppm was set to 10
105e, and do not allow it to flow into the reaction chamber (733).

After each flow rate stabilizes, the pressure in the reaction chamber (733) decreases to 1. The pressure control valve (745) was adjusted so that the pressure was ○Torr. On the other hand, the conductive substrate (752) on which the a-C film has been completely formed is heated to 240°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). 4 to the power application electrode (736)
A power of 5 Watts 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.

The obtained a-5i film was subjected to ○NH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 21 atomic % and the boron atoms were 11 atomic ppm based on the total constituent atoms.
, oxygen atoms were 0.31 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 -400V (+370V), 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 26 V/.mu.m (24 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

Also, the time required for dark decay from Vmax to 90% of Vmax in the dark is approximately 6 seconds (approximately 5 seconds).
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 4. Flux・
seconds (4°3 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.

In the previous 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. 4 control valves (70
7, 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 carbon tetrafluoride gas is supplied from the fourth tank (704) to 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 scale of the wJ device on each flow rate side to set the hydrogen gas flow rate to 180 seconds, the butadiene gas flow rate to 40 seconds, and the oxygen gas flow rate to 4 sccm.
The flow rate of s and 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, the conductive substrate (752) is 50 x 50 x 50 x 50 x 50 x 50 x 50
Using an aluminum substrate with a thickness of 3 mm, heat it to 180°C in advance.
After heating to , and with the gas flow and pressure stable,
Turn on the low frequency power supply (739) that has been connected in advance using the connection selection switch (744), and connect the power application electrode (741).
) was applied with a power of 200 Watts at a frequency of 700 KHz 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-CgQ obtained as described above, and the amount of hydrogen atoms contained was 4o at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, fluorine atoms, was 4.1 atomic % based on the total constituent atoms, and the amount of oxygen atoms was roughly 1.8 atomic % 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 third control valve (709), the fifth control valve (711), and the sixth control valve (712) are released, hydrogen gas is released from the first tank (701), tetrafluorosilane gas is removed from the third tank (703), Nitrous oxide gas is supplied from the fifth tank (705) and silane gas is supplied from the sixth tank (706) at an output pressure of IKg/
The first, third, fifth, and sixth flow controllers (under cm2)
713, 715, 717, and 718). At the same time, the fourth control valve (710) is opened, and diborane gas diluted to 1100 pp with hydrogen gas is supplied from the fourth tank (704) into the fourth flow rate controller (716) under an output pressure of 1°5 Kg/cm2. I let it flow. Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 200 sec, the flow rate of silane tetrafluoride gas to 50 sec, the flow rate of nitrous oxide gas to lsccms, and the flow rate of silane gas to 50 sec.
The flow rate of diborane gas diluted to 1100pp with hydrogen gas was set to 10105e, and the reaction chamber (73
3) It was allowed to flow into the interior. 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 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.

The obtained a-Si 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 22 at% of the total constituent atoms, and the boron atoms were 10 attom ppm.
The content of 5 fluorine atoms was 5 at%, and the content of oxygen atoms was 0.1 at%.

・Characteristics: When the obtained photoreceptor was used in a conventional Carlson process with both negative and positive charging, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -760V (+750V), 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 (49 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 15 seconds (approximately 17
seconds), and from this it was understood that it had 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 3.9 lux · seconds (3.3 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.

[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 3 Figure 5 Figure 2 Figure 4 Figure 6 Procedural amendment dated IO 21, 1985 1, Case Description 1988 Patent M1 No. (/-2') 1) No. 415 2, Name of the invention Photoreceptor 3, Relationship with the case of the person making the amendment Applicant address 2-30 Azuchi-cho, Higashi-ku, Osaka City Name of Osaka Kokusai Building (607) Mi/Ruta Camera Co., Ltd. 5, Subject of amendment Drawing 6, contents of amendment Drawing 8 will be corrected as shown in "Corrected Drawing 8".

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; Hydrogenated amorphous silicon film containing atoms and at least one of phosphorus atoms and boron atoms, or fluorinated amorphous silicon film containing oxygen atoms and at least one of phosphorus atoms and boron atoms A photoreceptor characterized by being a film.