JPS6382425A - Photosensitive body - Google Patents

Abstract

PURPOSE:To permit improvement in photosensitive characteristics and extreme reduction in film thickness by forming an electric charge transfer layer of a hydrogenated amorphous carbon film contg. nitrogen and halogen atoms and an electric charge generating layer of a hydrogenated or fluorinated amorphous silicon germanium film contg. 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 contg. the nitrogen atoms and halogen atoms and the charge generating layer 3 is formed of the hydrogenated or fluorinated amorphous silicon germanium a-Si film contg. at least either of the phosphorus atoms or boron atoms and the carbon atoms. The a-C film is formed to 5-50mu thickness and the content of N is specified to 5% and the content of halogens to 0.1-25%. The a-Si film is formed to 0.1-5mu thickness and the content of C is specified to 0.001-5% and the content of P or B to <=20,000ppm. The charge transfer layer 2 is thereby improved in transferability, electric chargeability, durable weatherability 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 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 telluride, cadmium sulfide, zinc oxide, amorphous silicon, polyvinyl carbazole, metal phthalocyanine,
Examples include organic substances such as disazo pigments, trisazo pigments, perylene pigments, triphenylmethane compounds, triphenylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, oxazole compounds, and oxadiazole compounds. In addition, the configurations include a single-layer structure in which these substances are used alone, a binder-type structure in which they are dispersed in a binder, and a laminated structure in which a charge generation layer and a charge transport layer are provided for each function. Can be mentioned.

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

In order to eliminate such drawbacks, in recent years, amorphous silicon produced by a glow discharge method has been increasingly applied to electrophotographic photoreceptors as a material with improved toxicity and high durability. However, while amorphous silicon requires a large amount of silane gas as a raw material, it is an expensive gas, so the resulting electrophotographic photoreceptor is also significantly more expensive than a conventional photoreceptor. In addition, there are many inconveniences in production, such as the slow film formation rate and the generation of explosive silane undecomposed products in the form of dust as the film formation time increases. Furthermore, if this dust gets mixed into the photosensitive layer during manufacturing, it will have a significant negative effect on image quality. 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. must 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.
1 of Applied Palyme
r 5science) Volume 17, pages 885 to 8
On page 92, it was also reported by the same author in the American Chemical Society in 1979 that all organic compounds can be made from gases.
Plasma Polymeri, published by Chemical Society
zation), its film formability is also discussed.

However, plasma organic polymer films prepared by conventional methods are used only for applications that assume insulation properties, that is, they are considered to be insulating films with a specific resistance of about 1016 Ωcm, like ordinary polyethylene films, or was used with the understanding that it was at least 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 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-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-5i. .

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 Recomba (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.

The day is about to end. ! As mentioned above, plasma organic polymer films conventionally used in electrophotographic photoreceptors have been used as so-called undercoat layers or overcoat layers, but these are films that do not require a carrier transport function. Therefore, organic polymer films are used based on the judgment that they are insulating. Therefore, it can only be used as an extremely thin film with a thickness of about 5 μm at most, and carriers either pass through the film by tunneling effect, or if a tunneling effect cannot be expected, there is virtually no problem with the generation of residual potential. It is only used in thin films that are only small enough to last. Further, the amorphous silicon films conventionally used in electrophotography are so-called thick films and are used up, and have 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 nitrogen atoms and halogen atoms. In some cases, when laminated with a hydrogenated or fluorinated amorphous silicon germanium film that contains at least one of phosphorus atoms and boron atoms and also contains carbon atoms, it has charge transport properties and is easily suitable for electrons. It was discovered that the material began to exhibit photographic properties. There are many points in the theoretical interpretation that are unclear even to the present inventor (although I cannot discuss them in detail, there are many points that are unclear even to the inventors). A band structure formed by electrons in a stable energy state, such as π electrons, unpaired electrons, residual free radicals, etc. Alternatively, since it has an energy level similar to the band structure formed by the fluorinated amorphous silicon germanium film in the conduction band or valence band, it contains at least one of phosphorus atoms and boron atoms and also contains carbon atoms. Carriers generated in the hydrogenated or fluorinated amorphous silicon germanium film are easily injected into the hydrogenated amorphous carbon film containing nitrogen atoms and halogen atoms, and these carriers are relatively unstable as described above. This is presumed to be because the hydrogenated amorphous carbon film containing nitrogen atoms and halogen atoms can travel suitably through the action of electrons in a certain energy state.

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 nitrogen 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 carbon atoms. An object of the present invention is to provide a photoreceptor using a thin film of amorphous silicon germanium as a charge generation layer.

Means for solving the problem, that is, 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 nitrogen atoms and halogen atoms generated from a plasma polymerization reaction. and a hydrogenated or fluorinated amorphous silicon germanium film in which the charge generation layer contains at least one of phosphorus atoms and boron atoms and also contains carbon atoms. (Hereinafter, the charge transport layer according to the present invention is an a-C film and the charge generation layer is an a-Si film.
(referred to as a membrane).

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 nitrogen atoms and halogen atoms generated by glow discharge as a charge transport layer, and a hydrogenated amorphous carbon film containing at least nitrogen atoms and halogen atoms generated by glow discharge as a charge generation layer. The present invention relates to a functionally separated photoreceptor characterized by being provided with a hydrogenated or fluorinated amorphous silicon germanium film containing at least one of boron atoms and carbon 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 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 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-CPA.

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

There are many types of hydrocarbons that can be used, but examples of saturated hydrocarbons include methane, ethane, propane, butane,
Pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane,
tocosan, tricosane, tetracosan, pentacosan,
Normal paraffins such as hexacosane, heptacosane, octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, etc., as well as isobutane, isopentane, neopentane, isohexane, neohexane, 2,3-dimethylbutane, 2-methylhexane, 3- Ethylbebutane, 2,2-dimethylpentane, 2
．． 4-dimethylpentane, 3.3-dimethylpentane,
Tributane, 2-methylhebutane, 3-methylhebutane, 2.2-dimethylhexane, 2,2.5-dimethylhexane, 2.2.3-trimethylpentane, 2.2.4
-) Isoparaffins such as dimethylpentane, 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- Olefins such as methyl-2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-nonene, 1-decene, and allene, methylalene, butadiene, pentadiene, hexadiene,
Diolefins such as cyclopentadiene, triolefins such as ocimene, allocimene, myrcene, hexatriene, acetylene, butadiyne, etc.
゜3-pentadiyne, 2.4-hexadiyne, methylallene, 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 Terpenes such as , cycloundecane, tricyclene, pisabolene, zingiberene, culu, cumene, humulene, cadinensesquivenichen, selinene, caryophyllene, santarene, cedrene, campholene, phylloclatene, bodocarbrene, mirene, and steroids are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, pseudocumene, mesitylene, prenitene, isodurene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene,
Biphenyl, terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

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

The amount of hydrogen atoms contained in the a-C film of the present invention is inevitably determined from the manufacturing aspect of using glow discharge, but it is approximately 30 to 60 atomic percent contained in the a-C film based on the total amount of carbon atoms and hydrogen atoms. Ru. Here, the content of carbon atoms and hydrogen atoms in the film is determined by 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
0 um, especially 7 to 20 um, is appropriate; if it is thinner than 5 um, the charging potential will be low, making it impossible to obtain a sufficient density of the copied image. Moreover, if it is thicker than 50 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 as mentioned above, even if the film thickness is 5 μm or more, carriers are not trapped and contribute to transport brightness attenuation. It is possible.

In the process of forming the a-C film from the raw material gas in the present invention, there 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. Most preferably, neutral particles may also be formed through an ion state 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, a nitrogen compound is used as a raw material for adding at least nitrogen atoms into the a-C film. The phase state of the nitrogen 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 nitrogen compounds used include inorganic compounds such as nitrogen and ammonia, organic compounds having functional groups such as amino groups (NH2) and cyano groups (-CN), and nitrogen-containing heterocycles.

There are many types of organic compounds that can be used, but examples of organic compounds that have an amino group include methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, and undecyl. amine,
Dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyamylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, allylamine, diallylamine, Triallylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, toluidine, benzylamine, dibenzylamine, tribenzylamine, diphenylamine, triphenylamine, naphthylamine , ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diaminohebutane, diaminooctane, diaminononane, diaminodecane, phenylenediamine, etc. are used. Examples of organic compounds having a cyano group include acetonitrile, propionitrile, butyronitrile, valeronitrile, capronitrile, enantonitrile, caprylonitrile, ferargonitrile, cabrinitrile, lauronitrile, palmitonitrile, stearonitrile, and crotonitrile. Nitrile, malonitrile, stearonitrile, daltarnitrile, adiponitrile, benzonitrile, tolnitrile, cyanogenated benzylcinnamate nitrile, naphthonitrile, cyanpyridine, etc. are used. Examples of the heterocyclic compound include virol,
Viroline, pyrrolidine, oxazole, thiazole, imidazole, imidacilline, imidazolidine, pyrazole, pyrazoline, pyrazolidine, triazole, tetrazole, pyridine, piperidine, oxazine, morpholine, thiazine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, indole, indoline, benzo oxazole, indazole, benzimidazole,
quinoline, cinnoline, phthalazine, phthalocyanine,
Quinazoline, quinxaline, carbazole, acridine, phenanthroline, phenazine, phenoxazine, indolizine, quinolidine, quinuclidine, napthyridine, purine, pteridine, aziridine, azepine, oxadiazine, dithiazine, benzoquinoline, imidazothiazole, and the like are used.

In the present invention, the amount of nitrogen atoms contained as a chemical modifier is 5.0 at % or less based on the total constituent atoms. Here, the content of nitrogen atoms in the film is determined by the usual method of elemental analysis.
For example, this can be determined by Auger analysis. If it does not contain nitrogen atoms, suitable transport properties cannot be ensured, the film formation rate is slow, and furthermore, it is likely to deteriorate over time after film formation.

On the other hand, when the amount of nitrogen atoms exceeds 5.0 at%,
When added in a small amount, nitrogen atoms, which ensure suitable transportability, instead exhibit an effect that lowers the resistance of the film, resulting in a decrease in charging ability. Therefore, the range of the amount of nitrogen added in the present invention is important.

In the present invention, the amount of nitrogen atoms contained as a chemical modifier can be controlled mainly by increasing or decreasing the amount of the nitrogen compound introduced into the reaction chamber in which the plasma reaction is performed. If the amount of nitrogen compounds introduced is increased,
It is possible to increase the amount of nitrogen atoms added into the a-C film according to the present invention, and conversely, by decreasing the amount of nitrogen compounds introduced, it is possible to increase the amount of nitrogen atoms added into the a-C film according to the present invention. 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 into the a-C film. 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 the α phase or the 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, bromine fluoride,
Iodine fluoride, hydrogen chloride, bromine chloride, iodine chloride, hydrogen bromide,
Inorganic compounds such as iodine bromide and hydrogen iodide, and organic compounds such as alkyl halides, aryl halides, styrene halides, polymethylene halides, 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, hebutyl chloride, hebutyl bromide, hebutyl iodide, octyl fluoride, octyl chloride, octyl bromide, octyl iodide, nonyl fluoride, nonyl chloride, nonyl bromide, nonyl iodide, fluoride Decyl, decyl chloride, decyl bromide, decyl iodide, etc. are used. As the aryl halide, for example,
Fluorobenzene, chlorobenzene, bromobenzene,
Iodobenzene, chlorotoluene, bromotoluene, chlornaphthalene, bromonaphthalene, etc. are used.

As the halogenated styrene, for example, chlorstyrene, bromustyrene, iodostyrene, fluorostyrene, etc. are used. As halogenated polymethylene,
For example, methylene chloride, methylene bromide, methylene iodide, ethylene chloride, ethylene bromide, ethylene iodide, trimethylene chloride, trimethylene bromide, trimethylene iodide, butane dichloride, butane dibromide, butane shoide, dichloride. Pentane, pentane dibromide, pentane dibromide, hexane dichloride, hexane dibromide, hexane dichloride, hebutane dichloride, hebutane dibromide, hebutane dichloride, octane dichloride, octane dibromide, shodate Octane dichloride, 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 that can be contained in the film can be determined by a conventional method of electric 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 the a-C film according to the present invention, and conversely, by decreasing the amount of halogen compound introduced, the amount of halogen atoms added to the a-C film according to the present invention can be increased. It is possible to reduce the amount of halogen atoms added to the Nyoru a-C film.

In the present invention, silane gas, disilane gas, or fluorinated silane gas is used to form the a-si film. 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, methane, ethane, ethylene, acetylene, propane, propylene, butane, butadiene, butadiyne, butene, carbon oxide, or carbon dioxide can be used as a raw material gas for incorporating carbon atoms as chemical modifiers into the film. A carbon compound gas such as carbon is used. Furthermore, germane gas is used to contain germanium atoms.

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

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

In the present invention, the amount of carbon atoms contained as a chemical modifier is from 0.001 to S atomic% based on the total constituent atoms.
It is. Here, the content of carbon 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 carbon atoms in the film is lower than 0.001 at%, the electric resistance value of the a-3T film decreases, and the electric field due to corona charging etc. is less likely to be applied to the a-3i film, and photoexcited carriers are It is not necessarily injected into the <ts-C film, which leads to a decrease in sensitivity. Furthermore, the charging ability is also reduced. When the content of carbon atoms in the film is higher than 5 at%, the electrical resistance value of the a-Si film becomes too high, resulting in a decrease in sensitivity due to a decrease in the generation efficiency of photoexcited carriers and a decrease in the carrier velocity. invite Therefore, the range of the amount of carbon atoms added in the present invention is important.

The amount of hydrogen atoms or fluorine atoms contained in the a-Si film of the present invention is necessarily determined from the manufacturing aspect of using glow discharge, but the total amount of silicon atoms and hydrogen atoms or silicon atoms and fluorine atoms On the other hand, the content 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 ONH analysis and Auger analysis.

The appropriate thickness of the a-Si film as the charge generation layer in the present invention is 0.1 to 5 μm for use in a normal electrophotographic process, and if it is thinner than 0.1 μm, light absorption is insufficient. As a result, sufficient charge generation is not performed, resulting in a decrease in sensitivity. Ma.

On the other hand, if it is thicker than 5 μm, it is not preferable in terms of productivity. This a-Si film has a rich charge generation ability, and in a laminated structure with the a-C film, which is the most characteristic feature of the present invention, the generated carriers can be injected into the a-C film with high efficiency. It is possible to contribute to brightness 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.

In the present invention, the amount of carbon atoms, phosphorus atoms, or boron atoms contained as chemical modifiers is mainly determined by the amount of carbon compound gas, phosphine gas, or diborane gas introduced into the reaction chamber in which the plasma reaction is performed. It can be controlled by increasing or decreasing the amount of introduced. By increasing the amount of carbon compound gas, phosphine gas, or diborane gas introduced, it is possible to increase the amount of carbon atoms, phosphorus atoms, or boron atoms added to the a-Si film according to the present invention. Possible, and conversely, if the amount of introduced carbon compound gas, phosphine gas, or diborane gas is reduced, a-5 according to the present invention:
19. It is possible to reduce the amount of carbon atoms, phosphorus atoms, or boron atoms added therein.

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

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

When the surface of the photoreceptor is positively charged with, for example, a corona charger, and then used for image exposure, the holes generated in the charge generation FJ (3) in FIG.
), electrons generated in the charge generation layer (3) travel through the charge transport layer (2) toward the photoreceptor surface, and in FIG. In this case, holes generated in the charge generation layer (3) travel toward the conductive substrate (1) through the charge transport layer (2) on the conductive substrate side, and at the same time, electrons generated in the charge generation layer (3) travel toward the conductive substrate (1). travels through the charge transport layer (2) on the front side towards the surface of the photoreceptor, forming an electrostatic latent image with proper 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 an alternative form.

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

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

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

The charge transport layer of the photoreceptor according to the present invention decomposes molecules in the gas phase by discharge under reduced pressure, and diffuses active neutral species or charged species contained in the generated plasma atmosphere onto the substrate, using electric force or magnetism. 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 tanks are the first to sixth control valves (707)
〜(712) and the first to sixth flow rate controllers (713)〜(
718). (719) to (721) in the figure
) are first to third containers filled with 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 controllers (722) to (724) for vaporization. Roughly speaking, each container has seventh to ninth control valves (725) to (727) and seventh to ninth flow rate controllers (727).
28) 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 are
Heat can be applied to the gas obtained by vaporizing the raw material compound, which is in a liquid or solid phase at room temperature, by an appropriately placed pipe heater (734) so as not to condense on the way. Inside the reaction chamber, there is a ground electrode (735) and a power application electrode (
736) are installed facing each other, and each electrode can be heated by an electrode heater (737). A high frequency power supply (739) and a low frequency power matching box (740) are connected to the power applying electrode (736) via a matching box for high frequency power (738).
), low frequency power supply (741), low pass filter (
A DC power source (743) is connected via a power source (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 by a cooling exclusion device (749), a mechanical booster pump (750), or an oil rotary pump (748). The exhaust gas is made safe and harmless by a suitable exclusion device (753) and then exhausted into the atmosphere. Regarding these exhaust system piping, the gas that is the vaporized raw material compound that was in the liquid or solid phase at room temperature is
Appropriately placed pipe heaters (
734), heat can be applied. Reaction chamber (73
3) can also be heated by the reaction chamber heater (751) for the same reason, and a conductive substrate (751) is placed on the electrodes arranged inside.
52) is installed. In FIG. 7, a conductive substrate (75
2) is fixed to the ground electrode (735),
They may be fixedly arranged on the power application electrode (736), or may be arranged 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 (83?) is arranged on the 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. II at the same time! The electrode and the conductive substrate fixedly disposed on the electrode are heated to a predetermined temperature using a polar heater. 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 structure from among the above-mentioned photoreceptor structures. The present apparatus or a separate apparatus may be used to provide the undercoat layer or the charge generation layer. Next, the first to sixth tanks and the first
The raw material gases are introduced into the reaction chamber from the third 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 maintained at a constant reduced pressure by the pressure regulating valve. After the gas flow rate is stabilized, a connection selection switch is used to select, for example, a high frequency power source, and high frequency power is applied to the power application electrode. A discharge is started between the two electrodes, and a solid phase film is formed on the substrate over time. The a-Si film or 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. Also,
Gradually change only the raw material gas flow rate while sustaining the discharge,
It is also possible to stack films with 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 thickening 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 described below with reference to Examples.

Cross trip 1 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 from the tank, nitrogen gas from the third tank (703), and nitrogen gas from the fourth tank (T.

4) Each output pressure of carbon tetrafluoride gas is 1.0 Kg/cm.
2, the first, third, and fourth flow controllers (713, 7
15, 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 the seventh flow rate controller (7
28) It was allowed to flow into the interior. Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 60 seconds, the styrene gas flow rate to 30 seconds, and the nitrogen gas flow rate to 8 seconds.
The flow rate of carbon tetrafluoride gas is set to 30 sec, and the main pipe (73
2) into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) reaches 2°0 To
The pressure regulating valve (745) was adjusted so that rr. On the other hand, as a conductive substrate (752), fir 50× horizontal 50×
Using a 3 mm thick aluminum substrate, preheat it to 180°C, and with the gas flow rate and pressure stable, turn on the low frequency power supply (741) that was previously connected using the connection selection switch (744). , power application electrode (736)
A power of 200 Watts was applied at a frequency of 170 KHz to perform a plasma polymerization reaction for about 50 minutes, thereby forming an a-C film with a thickness of 15 μm as a charge transport layer on the conductive substrate (752). After completing the film formation, stop applying power and
The control valve was closed and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 47 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, that is, fluorine atoms, was 6.1 atomic % based on the total constituent atoms, and the amount of nitrogen atoms was 2.1 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 second control valve (708), the fifth control valve (711), and the sixth control valve (712) are released, and the first tank (701) is opened.
hydrogen gas, germane gas from the second tank (702), methane gas from the fifth tank (705), and silane gas from the sixth tank (706), output pressure IKg/cm2.
Under the 1st, 2nd, 5th, and 6th flow control capital N (713
, 714, 717, and 718).

At the same time, the fourth control valve (710) is released and the fourth tank (
Diborane gas diluted to 1100 pp with hydrogen gas from 704) was flowed into the fourth flow rate controller (716) under an output pressure of 1.5 Kg/cm2. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec, the germane gas flow rate to 6S CCm%, and the methane gas flow rate to 1.
0105e, the flow rate of silane gas was set to 101005e, and the flow rate of diborane gas diluted to 1100 pp with hydrogen gas was set to 101005e, and these were 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 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. Power application electrode (736
) was applied with a power of 40 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 ONH analysis in metal (EMGA-1300 manufactured by Horiba), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 24 atomic % and the boron atoms were 95 atomic ppm based on the total constituent atoms.
, carbon atoms are 1.0 at%, germanium atoms are 10.
It was 5 at%.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -700V (+660V), that is,
Since the total thickness of the photoreceptor M was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 46 V/.mu.m (43 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 16 seconds).
It was understood from this 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 1.8 lux·sec (2.9 lux・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 the commonly used Carlson process, a clear image was obtained.

Example 2 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 on the head.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. 4th control valve (70
7, 708, 709, and 71O), hydrogen gas from the first tank (701), air gas from the second tank (702), nitrous oxide 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 scale of each flow rate controller to set the flow rate of hydrogen gas to 60 seconds, the flow rate of ethylene gas to 60 seconds, and the flow rate of nitrous oxide gas to 16 seconds.
cm, and the flow rate of carbon tetrachloride gas was set to be 20 seconds, 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 2°0 Torr. On the other hand, as the conductive substrate (752), an aluminum substrate measuring 50 mm x 50 mm x 3 mm in thickness was used.
After heating to 0°C and with the gas flow rate and pressure stable, turn on the high frequency power supply (739) that was previously connected using the connection selection switch f (744), and connect the power application electrode (
736) with a power of 200 Watts at a frequency of 13.56M.
A plasma polymerization reaction was performed for about 5 hours by applying a voltage of Hz 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-CM obtained as described above, and the amount of hydrogen atoms contained was 43 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of atoms, that is, the amount of chlorine atoms was 5.0 at % based on the total constituent atoms, and the amount of nitrogen 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 fifth control valve (711L) and the sixth control valve (712) are released, and hydrogen gas is transferred from the first tank (701) to the second tank (711L).
germane gas from the fifth tank (702), ethane gas from the fifth tank (705), and silane gas from the sixth tank (706) through the first, second, fifth, and sixth flow rate controllers ( 713, 714, 717, and 71
8) It was allowed to flow into the interior. At the same time, the fourth control valve (710) is released and hydrogen gas is supplied from the fourth tank (704) to 1,100 yen.
Diborane gas diluted to PP is output at an output pressure of 1.5 kg/
do not flow into the fourth flow controller (716) under am2. Adjust the scale of each flow rate controller to increase the hydrogen gas flow rate to 2.
00sec.

The flow rate of germane gas was set to 10105e, the flow rate of ethane gas was set to 3 seconds, the flow rate of silane gas was set to 1001005c, and the flow rate of diborane gas diluted to 1100 pp with hydrogen gas was set to 10105e, and the flow rates were made to flow into the reaction chamber (733). After each flow rate stabilizes, the pressure regulating valve (74) is adjusted so that the pressure in the reaction chamber (733) becomes 0.9 Torr.
5) was adjusted. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 240°C, and the high-frequency power source (739) is heated to stabilize the gas flow rate and pressure.
The power application electrode (73
6), a power of 45 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-3i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Horiba), Auger analysis, and I
According to MA analysis, the hydrogen atoms that can be contained are 21 at% of the total constituent atoms, and the boron atoms are 11 at ppm.
1 carbon atom is 0.3 at%, germanium atom is 15.
It was 7 at%.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -570V (+570V), 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 37 V/.mu.m (37 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 Vmax of 9096 in the dark was approximately 14 seconds (approximately 1
3 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 1.5 lux · seconds (1.3 lux · seconds), and from this it was understood that it had sufficient photosensitivity performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using semiconductor laser light (emission wavelength 780 nm).The required light amount was 9.6.
erg/cm2 (7.5 erg/cm2), and from this it was understood that it had sufficient long wavelength light sensitivity performance.

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

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

Using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided 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 710), hydrogen gas from the first tank (701), acetylene gas from the second tank (702), nitrogen 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 1908 ccm, the acetylene gas flow rate to 45 seconds, and the nitrogen gas flow rate to 7 seconds.
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, as the conductive substrate (752), *5OX horizontal 50
Using an aluminum substrate with a thickness of 3 mm, heat it to 200°C in advance.
After heating to , and with the gas flow and pressure stable,
Turn on the cavity frequency power source (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 perform a plasma polymerization reaction for about 2 hours and 40 minutes 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, that is, fluorine atoms, is 2. Roughly speaking, the amount of nitrogen atoms was 1.1 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 second control valve (708), the fifth adjustment valve (711), and the sixth control valve (712) are released, hydrogen gas is released from the first tank (701), Germanic gas is removed from the second tank (702),
Methane gas from the fifth tank (705) and silane gas from the sixth tank (706) are supplied to the first, second, fifth, and sixth flow rate controllers (713,
714, 717, and 718).

At the same time, the fourth control valve (710) is released and the fourth tank (
Diborane gas diluted to 100 ppm with hydrogen gas from 704) was added to the fourth diborane gas under an output pressure of 1.5 kg/cm2.
It was made to flow into the flow rate controller (716). Adjust the scale of each flow rate control device to adjust the flow rate of hydrogen gas to 200 sec1
The flow rate of germane gas is 63CCm, and the flow rate of methane gas is 63CCm.
Quantity: 0.01secms Silane gas flow rate: 10100
5e, the flow rate of diborane gas diluted to 100 ppm with hydrogen gas was set to 10105e, and was allowed to flow 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, a-C
The conductive substrate (752) on which the film is formed is heated to 250°C.
After heating to , and with the gas flow and pressure stable,
A power of 35 Watts is applied to the power application electrode (736) at a frequency of 13.56 MHz from the high frequency power source (739), and no glow discharge is generated. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-3i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 20 at% of the total constituent atoms, and the boron atoms were 9 at pPms.
Carbon atoms are 0.001 at%, germanium atoms are 9.
It was 8 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 -580V (+660V), 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 38 V/.mu.m (43 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 19 seconds (approximately 20 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 3.1 lux·sec (2.8 lux・seconds), and from this we can understand that it has sufficient photosensitivity performance.

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

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

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. 4 control valve (707
, 708, 709, and 710), hydrogen gas from the first tank (701), butadiene gas from the second tank (702), ammonia gas from the third tank (703), and hydrogen gas from the fourth tank (704). Carbon fluoride gas was supplied to the first, second, third, and
and fourth flow rate controller (713, 714, 715, and 7
16) It was allowed to flow into the interior. Then, adjust the scales of each flow rate controller to set the flow rate of hydrogen gas to 120 sCCm1, the flow rate of butadiene gas to 60 scm, and the flow rate of ammonia gas to 60 sCCm.
s c crn % and the flow rate of carbon tetrafluoride gas is 1
Set it so that it is 60 sec, and mixer (73
1) and flowed into the reaction chamber (733) from the main pipe (732).

After each flow rate stabilizes, the pressure inside the reaction chamber (733) decreases to 2. The pressure control valve (745) was adjusted so that it became ITorr. On the other hand, as the conductive substrate (752), fir 5
Using an aluminum substrate measuring 0 x width 50 x thickness 3 mm, it was preheated to 120°C, and with the gas flow rate and pressure stabilized, a low frequency power source ( 741) and apply 140W of power to the power application electrode (736) at a frequency of 600K.
Plasma polymerization reaction was carried out for about 1 hour and 20 minutes by applying the voltage under Hz, and a 15 μm thick a-
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 51 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, fluorine atoms, was 19.0 at% based on the total constituent atoms, and the amount of nitrogen atoms was roughly 2.4 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),
Release the second control valve (708), the third control valve (7o9), the fifth control valve (711), and the sixth control valve (712),
Hydrogen gas from the first tank (701), hydrogen gas from the second tank (70
2), germane gas from the third tank (703), tetrafluoride silane gas from the fifth tank (705), and silane gas from the sixth tank (706) under an output pressure of IKg/cm2. into the first, second, third, fifth, and sixth flow controllers (713, 714, 715, 717, and 718). At the same time, the fourth control valve (71
0) and 1 with hydrogen gas from the fourth tank (704).
Diborane gas diluted to 100pp is heated to an output pressure of 1.5
Do not allow it to flow into the fourth flow rate limiting tFI device (716) under Kg/am2. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200sec and the germane gas flow rate to 3sec.
cm, the flow rate of silane tetrafluoride gas to 50 sec, the flow rate of carbon tetrafluoride gas to O,lscem, the flow rate of silane gas to 50 scem, and the flow rate of diborane gas diluted to 1100 pp with hydrogen gas to 10105e,
It was made to flow 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 0.9 Torr. On the other hand, a
- The conductive substrate (752) on which the C film is completely formed is 2
Heated to 50℃, and with the gas flow rate and pressure stable, a high frequency N source (739) was used to generate a frequency of 13.56MH.
z, a power of 35 Watt 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 Ltm.

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 11 at ppm.
, fluorine atoms are 4.8 at%, carbon atoms are 0.1 at%,
Germanium atoms were 6.4 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 at the time of positive charging are shown in parentheses, and the highest charging potential is -330V (+340V), 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 22 V/.mu.m (22 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 5 seconds (approximately 4 seconds), which indicates that it has charge retention performance that poses no practical problems. was understood. 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 4.4 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.

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 71Q), hydrogen gas from the first tank (701), butadiene gas from the second tank (702), nitrogen gas from the third tank (703), and nitrogen gas from the fourth link (704). The first, second, third, and fourth flow rate controllers (713, 714, 715, and 716) supply carbon tetrafluoride gas under an output pressure of 1.0 Kg/cm, respectively.
It flowed inside. Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 180 sec, the butadiene gas flow rate to 40 sec, and the nitrogen gas flow rate to 75 CCm.
The flow rate of N 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, as a conductive substrate (752), 1u50X horizontal 5
Using an aluminum substrate with a thickness of 3 mm,
℃, and with the gas flow rate and pressure stable, turn on the low frequency power supply (741) that was previously connected using the connection selection switch (744), and connect the power application electrode (73).
6), a plasma polymerization reaction was carried out for about 30 minutes by applying a power of 200 Watts at a frequency of 300 KHz 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 40 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, that is, fluorine atoms, was 4.1 at% based on the total constituent atoms, and the amount of nitrogen atoms was 1.8 at% based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
The second control valve (70B), the fifth boiling valve (711), and the sixth control valve (712) are opened, hydrogen gas is released from the first tank (701), germane gas is removed from the second tank (702),
Methane gas from the fifth tank (705) and silane gas from the sixth tank (706) are supplied to the first, second, fifth, and sixth flow rate controllers (713,
714, 717, and 718).

At the same time, the fourth control valve (710) is released and the fourth tank (
Phosphine gas diluted to 10 ppm with hydrogen gas (704) was flowed into the fourth flow rate controller (716) under an output pressure of 1.5 Kg/cm2. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec, germane gas flow rate to 6 sec, and methane gas flow rate to 3 sec.
The flow rate of cms silane gas is 200 sec, and the flow rate of phosphine gas diluted to 1100 pp with hydrogen gas is 10 sec.
105e 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, the conductive substrate (752) on which the a-C film is formed is heated to 230°C, and with the gas flow rate and pressure stable, it is heated at a frequency of 13°56MHz from a high frequency power source (739). 3 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.

On the obtained a-3i film, ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho) 1. When t-ditechnical analysis and IMA analysis were performed, the hydrogen atoms contained were 18 at % and the phosphorus atoms were 12 at ppm based on the total constituent atoms.
, carbon atoms are 0.3 at%, germanium atoms are 10.
It was 4 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 -500V (+760V), that is,
Since the total photoreceptor film thickness is 15°3μm, the charging capacity per μm is extremely high at 33μ/μm (49V/μm).
From this, it can be understood that it has sufficient charging performance.

In addition, I! from Vmax to 90% of Vmax surface potential in the dark! #The time required for decay was approximately 13 seconds (approximately 19 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 1.9 lux·sec (6.5 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 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 nitrogen atoms and halogen atoms; Hydrogenated amorphous silicon germanium film containing atoms and at least one of phosphorus atoms and boron atoms, or fluorinated amorphous film containing carbon atoms and at least one of phosphorus atoms and boron atoms A photoreceptor characterized by having a silicon germanium film.