JPS6381487A - Photosensitive body - Google Patents

Abstract

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

Description

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

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

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

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

In order to eliminate such drawbacks, in recent years, amorphous silicon produced by a glow discharge method has been increasingly applied to electrophotographic photoreceptors as a material with improved toxicity and high durability. However, while amorphous silicon requires a large amount of silane gas as a raw material, it is an expensive gas, so the resulting electrophotographic photoreceptor is also significantly more expensive than a conventional photoreceptor. In addition, there are many inconveniences in production, such as the slow film formation rate and the generation of explosive silane undecomposed products in the form of dust as the film formation time increases. Furthermore, if this dust gets mixed into the photosensitive layer during manufacturing, it will have a significant negative effect on image quality. Furthermore, amorphous silicon inherently has a high specific charge rate and therefore has low 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. 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 (Journa Be1l), published in 1973.
l of App l ied P.

lymer Sc 1ence) Volume 17, No. 885
Pages 892 to 892, it is also reported by the same author in 1979 that any organic compound can be prepared from gas.
American Chemical Society (America)
Plasma Po
lymerization), its film formability has been discussed.

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

For example, JP-A-59-28161 discloses a photoreceptor in which a plasma-polymerized polymer layer having a network structure is provided on a substrate as a blocking layer and an adhesive layer, and an amorphous silicon layer is provided thereon. ing. Japanese Patent Application Publication No. 5
Publication No. 9-38753 discloses that a high resistance plasma polymerized film of 1013 to 1Q15 Ωcm 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-3i
However, it does not solve the above-mentioned essential problems.

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

JP-A-60-249115 discloses that 0.05 to 5μ
A technique 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-3i.

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

Philosophical Magazine (Philosophical Magazine) published in 1976 by
Since it was reported in Vol. 33, pages 935 to 949 of I Magaz 1ne) that polar cavities are possible materials, attempts have been made to apply them to various photoelectric devices. Regarding application to photoreceptors, for example, JP-A-56-62254, JP-A-57-119356, JP-A-57-177147, JP-A-57-
119357, JP 57-177149, JP 57-119357, JP 57-17
7146, JP 57-177148, JP 57-174448, JP 57-1744
No. 49, JP-A-57-174450, etc.
Amorphous silicon photoreceptors containing carbon atoms have been disclosed, but all of them are aimed at adjusting the photoconductivity of amorphous silicon with carbon atoms.
Furthermore, amorphous silicon itself requires a thick film.

Problems to be Solved by the Invention 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 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. 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 nitrogen atoms and halogen atoms. In some cases, when laminated with a hydrogenated or fluorinated amorphous silicon germanium film containing at least one of phosphorus atoms and boron atoms and nitrogen atoms, it has charge transport properties and can easily become a suitable electron source. It was discovered that the material began to exhibit photographic properties. There are many unclear points in the theoretical interpretation, even for the present inventor, and it is not possible to discuss it in detail, but the relatively unstable hydrogenated amorphous carbon film containing nitrogen atoms and halogen atoms is Hydrogenated or fluorine in which the band structure formed by electrons in a certain energy state, such as π electrons, unpaired electrons, residual free radicals, etc., contains at least one of a phosphorus atom and a boron atom and also a nitrogen atom. Hydrogenated or The carriers generated in the fluorinated amorphous silicon germanium film are easily injected into the hydrogenated amorphous carbon film containing nitrogen atoms and halogen atoms, and these carriers are in the relatively unstable energy state mentioned above. It is presumed that this is because the hydrogenated amorphous carbon film containing nitrogen atoms and halogen atoms can travel suitably through the action of electrons.

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 nitrogen atoms. The present invention aims 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. a hydrogenated amorphous carbon film containing hydrogenated or fluorinated amorphous silicon germanium film, and the charge generation layer contains at least one of phosphorus atoms and boron atoms and nitrogen atoms. Regarding an electrophotographic photoreceptor (hereinafter referred to as
The charge transport layer according to the present invention is referred to as an a-C film and the charge generation layer is referred to as a-3ilf*).

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 created to solve these problems.

That is, the present invention provides a hydrogenated amorphous carbon film containing at least nitrogen atoms and halogen atoms produced by glow discharge as a charge transport layer, and a hydrogenated amorphous carbon film containing at least nitrogen 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 germanium film containing at least one of atoms and boron atoms and nitrogen 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 aC film.

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

There are many types of hydrocarbons that can be used, but examples of saturated hydrocarbons include methane, ethane, propane, butane,
Pentane, hexane, heptane, octane, nonane, decane, undecane, tridecane, tridecane, tetradecane, bentatecane, hexadecane, heptadecane,
Normal paraffins such as octadecane, nonatecane, eicosane, heneicosane, tocosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, 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,
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, isobutylene, 1-butene, 2-butene, 1-pentene, 2-
Pentene, 2-methyl-1-butene, 3-methyl-1-
Butene, 2-methyl-2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-
Olefins such as nonene, 1-decene, diolefins such as allene, methylalene, butadiene, pentadiene, hexadiene, cyclopentadiene, and triolefins such as ocimene, alloocimene, myrcene, hexatriene, and Acetylene, butadiyne, 1゜3-pentadiyne, 2,4-hexadiyne, methylallenene, 1-nonane, 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, cycloundecane, cycloundecane, cycloparaffin, cyclopentadecane, cyclohexadecane, etc. cycloparaffins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, and cycloolefins such as limonene, tervirun, phelandrene, sylvestrene, thuen, carene, pinene, bornylene, kanghuen, fuenchen, Terpenes such as cycloundecane, tricyclene, pisabolene, zingiberene, curcumene, 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 at% of the total amount of carbon atoms and hydrogen atoms. . Here, the content of carbon atoms and hydrogen atoms in the film is determined by a conventional method of organic elemental analysis, for example, CN
This can be determined by using H analysis.

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

The thickness of the a-C film as the charge transport layer in the present invention is 5 to 5
A thickness of 0 .mu.m, especially 7 to 20 .mu.m, is suitable; if it is thinner than 5 .mu.m, 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 even if the film thickness is 5 μm or more as mentioned above, carriers are transported without being trapped and contribute to bright attenuation. is possible.

In the process of forming an a-C film from a raw material gas in the present invention, the raw gas is formed through a plasma state generated by a plasma method using direct current, low frequency, high frequency, microwave, etc. The most preferable method is to form the ionized state by an ionization vapor deposition method, an ion beam evaporation method, or the like.
It may be formed from neutral particles produced by a vacuum evaporation method, a sputtering method, or the like, or it may be formed by a combination thereof.

In the present invention, in addition to hydrocarbons, a -C1l! A nitrogen compound is used as a raw material for adding a small amount of nitrogen atoms to J.The phase state of the nitrogen compound does not necessarily have to be a gas phase at room temperature and normal pressure; As long as it can be vaporized through evaporation, sublimation, etc., it can be used in either liquid or solid phase. Examples of nitrogen compounds include nitrogen, inorganic compounds such as ammonia, amino groups (NH2), cyano groups (- Organic compounds having functional groups such as CN), nitrogen-containing heterocycles, and the like are used.

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, benzylamine, 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, deazole, imidazole, imidacilline, imidapridine, pyrazole, pyrazoline, pyrazolidine, triazole, tetrazole, pyridine, piperidine, oxazine, morpholine, thiazine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, indole, indoline, benzoxazole , indazole, benzimidazole,
quinoline, cinnoline, phthalazine, phthalocyanine,
Quinazoline, quinxaline, carbazole, acridine, phenanthridine, 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 are not ensured, the film formation rate is slow, and furthermore, it tends to deteriorate over time after film formation. On the other hand, when the amount of nitrogen atoms exceeds 5.0 at%, the nitrogen atoms, which had ensured suitable transport properties when added in small amounts, conversely exhibit the effect of lowering the resistance of the film, causing charging performance. will decrease. 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; as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure, it can be used in either a superficial or solid phase. 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, and iodine bromide. , hydrogen iodide, and other inorganic compounds; and organic compounds such as alkyl halides, aryl halides, styrene halides, polymethylene halides, and haloforms. 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, butyl iodide, butyl fluoride, butyl chloride, butyl bromide, butyl iodide, amyl fluoride, amyl chloride, amyl bromide,
amyl iodide, hexyl fluoride, hexyl chloride, hexyl bromide, hexyl iodide, hexyl fluoride, hexyl chloride, hebutyl bromide, hexyl 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, 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. As the haloform, for example, fluoroform, chloroform, bromoform, iodoform, etc. are used.

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 cannot be 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, it is possible to increase the amount of halogen atoms added to the a-C film according to the present invention. It is possible to reduce the amount of halogen atoms added to the a-C film.

In the present invention, silane gas, disilane gas, or fluorinated silane gas is used to form the aSr 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, a nitrogen compound gas such as nitrogen gas, ammonia gas, nitrous oxide gas, or nitrogen dioxide gas is used as a raw material gas for containing nitrogen atoms as a chemical modifier in the film. . Furthermore, germane gas is used to contain germanium atoms.

The content of germanium atoms contained in the a-5i film in the present invention is preferably 30 at % or less with respect to the total of silicon atoms and germanium atoms. Here, the contents of germanium atoms and silicon atoms can be determined by a conventional method of elemental analysis, for example, Auger analysis. The content of germanium atoms can be increased by increasing the flow rate of germane gas flowing during film formation. As the content of germanium atoms increases, the long wavelength sensitivity of the photoreceptor of the present invention improves, and exposure sources can be selected from a wide range from short wavelength regions to long wavelength regions, which is preferable. Excessive addition is not preferable since a large content will lead to a decrease in charging ability. Therefore, the content of germanium atoms that can be 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 nitrogen atoms contained as a chemical modifier is 0.001 to 3 at% based on the total constituent atoms.
It is. Here, the content of nitrogen 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 nitrogen atoms in the film is lower than 0.001 at%, the electrical resistance of the a-3i film decreases, making it difficult for electric fields to be applied to the a-Si film due to corona charging, etc., and photoexcited carriers are This does not necessarily mean that the efficiency is lower than that of the a-C film, resulting in a decrease in sensitivity. Furthermore, the charging ability is also reduced. When the content of nitrogen atoms in the film is higher than 3 at%, the nitrogen atoms that were added in a small amount ensured suitable charging ability, but when added in excess, the a-Si film becomes highly resistive and becomes easily charged. This causes a decrease in sensitivity due to a decrease in the degree of movement.

Therefore, the range of the amount of nitrogen 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.

H'J of a-3i film as charge generation layer in the present invention
For use in normal electrophotographic processes, a thickness of 0.
A suitable thickness is 1 to 5 .mu.m, and if it is thinner than 0.1 .mu.m, light absorption will be insufficient and sufficient charge generation will not be carried out, leading to a decrease in sensitivity. Moreover, if it is thicker than 5 μm, it is not preferable in terms of productivity. This a-3i film is rich in charge generation ability, and is roughly the most characteristic feature of the present invention.
In the laminated structure with J, it is possible to efficiently inject generated carriers into the a-C film and contribute to suitable bright attenuation.

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

In the present invention, the amount of nitrogen atoms, phosphorus atoms, or boron atoms that can be contained as chemical modifiers is determined mainly by the amount of the nitrogen 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 introduced. By increasing the amount of nitrogen compound gas, phosphine gas, or diborane gas introduced, nitrogen atoms, phosphorus atoms,
Alternatively, it is possible to increase the amount of - elementary atoms added,
Conversely, if the amount of nitrogen compound gas, phosphine gas, or diborane gas introduced is reduced, the amount of nitrogen 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 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) and a charge generation P! on a conductive substrate (1). (3) and charge transport FJ
This figure shows a structure in which (2) is 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-3i 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 CM'J, there is no need to provide a surface protective layer, but for the purpose of adjusting the consistency with various elements in a copying machine, such as preventing staining of the photoreceptor surface due to adhesion of developer, the surface Providing a protective layer 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 a-8ilf4, so in most cases adhesiveness and injection blocking effect are ensured. Therefore, it is preferable to provide an intermediate layer. Figures 1 and 3
In the case of the configuration shown in the figure, the bonding surface with the conductive substrate has adhesive properties and
Since the charge transport layer according to the present invention has an excellent injection blocking effect, there is no need to provide an intermediate layer, but it may be necessary to compatibility with the manufacturing process before forming the photosensitive layer, such as the pretreatment method of the conductive substrate. For the purpose of adjusting properties, providing an intermediate layer can also be a further form.

FIG. 6 shows, as a rough form, an intermediate N (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 a gas phase by discharge decomposition under reduced pressure, and diffuses active neutral species or charged electrodes contained in the generated plasma atmosphere onto the substrate, using electric force or magnetism. It is preferable that the material be generated by a so-called plasma polymerization reaction, in which the material is introduced by force or the like and deposited as a solid phase by a recombination reaction on the 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 phase at room temperature, and each container is heated by the first to third temperature regulators (7 and 2) to (724) for vaporization. Heating is possible, and each container is connected to seventh to ninth control valves (725) to (727) and seventh to ninth tC quantity control devices (728) to (730). . After these gases are mixed in the mixer (731), the main pipe (732)
It is sent into the reaction chamber (733) via. 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 low frequency power matching box (738) via a high frequency power matching box (738).
A low frequency power source (741) is connected via a low-frequency power source (741) through a low-pass filter (742), and a DC power source (743) is connected through a low-pass filter (742), and power with different frequencies can be applied by a connection selection switch (744). The pressure inside the reaction chamber (733) can be adjusted by a pressure control valve (745), and the pressure inside the reaction chamber (733) can be reduced through an exhaust system selection valve (746), a diffusion pump (747), and an oil rotary valve. Pump (74
8), or cooling exclusion device (749), mechanical booster pump (750), oil rotary pump (748)
This is done by The exhaust gas is made safe and harmless by a suitable exclusion device (753) and then exhausted into the atmosphere. These exhaust system piping can also be heated and cleaned by appropriately placed piping heaters (734) to prevent the vaporized gas from the raw material compound, which is in a liquid or solid phase state at room temperature, from condensing on the way. ing. 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 arranged on the ground electrode (735), but 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) Is there grounding inside as shown in Figure 7? If pole (735)
A cylindrical conductive substrate (852) that also serves as a cylindrical conductive substrate (852) is installed, and an electrode heater (837) is arranged inside. Around the conductive substrate (852), there is also a circular power application circuit.
An R pole (836) is arranged, and an electrode heater (837) is placed on the outside.
) are arranged. 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 gas is introduced into the reaction chamber from the first to sixth tanks and the first to third containers while being kept at a constant flow using the first to ninth flow control devices as appropriate, and the pressure control valve is used to maintain a constant flow inside the reaction chamber. Maintain a reduced pressure. After the gas flow rate is stabilized, the connection selection switch selects, for example, a high frequency N 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 continuing 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 described below with reference to Examples.

Great journey, using the manufacturing device according to the present invention, as shown in Figure 1,
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Fourth control valve (7
07, 708, 709, and 710), hydrogen gas from the first tank (701), acetylene gas from the second tank (702), 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) Don't let it flow inside. Then, adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 190 seconds, 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) increases to 2.0T.
The pressure control valve (745) was adjusted so that the

On the other hand, as the conductive substrate (752),
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 high frequency power supply (739) that has been connected in advance using the connection selection switch (744), and apply power to the 'IIl pole (
736) at a frequency of 200 Watts at pH 3,56
Plasma polymerization reaction was carried out under MHz 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 is completed,
The application of electric power 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-CMI 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 nitrogen atoms was roughly 1.1 at% based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks were replaced and the first FAfS valve (707
), the second control valve (708), the fifth control valve (711), and the sixth control valve (712) are opened, and the first tank (701
) from the second tank (702), germane gas from the second tank (702), and the fifth tank (T.

5) and silane gas from the sixth tank (706) to the first, second, fifth, and sixth flow rate controllers (713, 714, 717,
and 718). At the same time, the fourth control valve (7
10) is released, and phosphine gas diluted to 10 ppm with hydrogen gas is supplied from the fourth tank (704) at an output pressure of 1.
into the fourth flow controller (716) under 5Kg/am2;
I let it flow in.

Adjust the scale of each flow ffi controller to increase the hydrogen gas flow rate to 2.
00sec, germane gas flow rate 6sec1 nitrogen gas flow rate 3secms, silane gas flow rate 200s
ecm, the flow rate of phosphine gas diluted to 1100 pp with hydrogen gas was set to 1 Osccm, and the reaction chamber (73
3) Don't let it flow inside.

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, the conductive substrate (752) on which the a-C film is formed is heated to 250°C, and is heated to 13.56 MH2 from a high frequency power source (739) under a stable gas flow rate and pressure. Power application 74 poles (736)
A power of 35 Watts was applied to generate a gummy 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 ○NH analysis in metal (EMGA-1300 manufactured by Miba Seisakusho), Auger analysis, and I
MA analysis revealed that the hydrogen atoms contained were 18 at% and the phosphorus atoms were 12 at.ppm5 based on the total constituent atoms.
Nitrogen atoms are 0.3 at%, germanium atoms are 10.0
It was 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 -580V (+860V), 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 (56 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 31 seconds (approximately 29 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the R high potential using white light, and the amount of light required was 2.5 lux seconds (8,2 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.

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

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Fourth control valve (7
07, 708, 709, and 710), hydrogen gas from the first tank (701), ethylene gas from the second tank (702), nitrous oxide gas from the third tank (703), and hydrogen gas from the fourth tank (704). ), carbon tetrachloride gas was supplied to the first, second, and third stations under an output pressure of 1-OKg/cm2, respectively.
, and into the fourth flow rate controllers (713, 714, 715, and 716). Then, adjust the scales of each flow rate controller to set the tC amount of hydrogen gas to 60 seconds, the flow rate of ethylene gas to 60 seconds, and the flow rate of nitrous oxide gas to 1.
6 sec, and the flow rate of carbon tetrachloride gas is 20 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 2°0 Torr. On the other hand, as the conductive substrate (752), fir 5
Using an aluminum substrate of 0 x width 50 x thickness 3 mm, it was preheated to 240°C, and with the gas flow rate and pressure stable, a high frequency Ti source (739) was connected in advance using the connection selection switch (744). ) and applied 200 Watt power to the power application electrode (736) at a frequency of 13.
A plasma polymerization reaction was performed for about 8 hours by applying a frequency of 56 MHz, 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 it was found that the amount of hydrogen atoms that could be 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 second control valve (708), the fifth control valve (711), and the sixth control valve (712) are released, hydrogen gas is released from the first tank (701), germane gas is removed from the second tank (702),
Nitrogen gas from the fifth tank (705) and the sixth tank (
706) under the output pressure IKg/cm2 through the first, second, fifth, and sixth flow rate controls tjKJN (7
13,714,717, 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 (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.
secm, germane gas flow rate 6 sec.

The flow rate of nitrogen gas was set to O1secms, 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 10105e, and these were flowed into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) becomes 0.8To
The pressure regulating valve (745) was adjusted so that rr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 250°C, and with the gas flow rate and pressure stable, a high frequency power source (739) is applied to the conductive substrate (752) at a frequency of 13.56.
A power of 35 Watt was applied to the power application electrode (736) under MHz to generate glow discharge. This discharge is 5
This was carried out for a minute 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), Auger analysis, and I
According to MA analysis, the hydrogen atoms that can be contained are 23 at.% of the total constituent atoms, and the boron atoms are 10 at.ppm.
, nitrogen atoms are O0○01 at%, germanium atoms are 1
It was 1 atomic %.

Characteristics: When the fFJ photoreceptor was used in a conventional Carlson process with both negative and positive charging, the following performance was obtained. Here, the measured values when positively charged are shown in parentheses.
The highest charging potential is -520V (+480V), that is, since the total photoreceptor film thickness is 15°3μm, it is 1μm.
The charging capacity per charge was extremely high at 34 .mu.m/.mu.m (32 V/.mu.m), and from this it was understood that it had sufficient W':4 performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 13 seconds (approximately 14 seconds).
seconds), and from this fact it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential, and the amount of light required was 1.3 lux · seconds (1.2 lux · seconds), and from this it was understood that it had sufficient photosensitivity performance. Also, after initial charging to the highest charging potential, what is the required amount of light to attenuate the surface potential to 20% of the highest charging potential using semiconductor laser light (emission wavelength 780 nm)? ,8e
rg/cm2 (7.5 erg/am2), 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.

By using the manufacturing apparatus according to the present invention, as shown in FIG. 1,
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, nitrogen 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. It was made to flow into the Il vessels (713, 715, and 716).

At the same time, the styrene gas from the first container (719) is heated to the first temperature control! (722) The 7th flow rate suppressor at a temperature of 35℃ (
728). Then, the scales of each flow rate controller were adjusted to set the hydrogen gas flow rate to 60 seconds and the styrene gas flow rate to 30 seconds.

The flow rate of nitrogen gas was set to 8 seconds and the flow rate of carbon tetrafluoride gas was set to 30 seconds.
731) from the reaction chamber (733) from the main pipe (732).
) flowed into the interior. After each flow rate stabilizes, the reaction chamber (
The pressure regulating valve (745) was adjusted so that the pressure inside the tube (733) was 2°0 Torr. On the other hand, a conductive substrate (752
), use an aluminum board measuring u50x width 50x 3mm thick, heat it to 180℃ in advance, and with the gas flow rate and pressure stable, connect the connection selection switch (7mm) in advance.
44), the low frequency power source (741) connected to the conductive substrate ( 752) Thick 15 on top
A μm a-C film was formed as a charge transport layer. After the film formation is completed, stop applying power, close the control valve, and close the reaction chamber (7
33) Thoroughly evacuated the inside.

Organic elemental analysis was performed on the a-C film obtained as described above, and it was found that the amount of hydrogen atoms that could be contained was 47 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of atoms, ie, fluorine atoms, was 6.1 atomic % based on the total constituent atoms, and roughly, 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 opened, hydrogen gas is released from the first tank (701), germane gas is removed from the second tank (702),
Ammonia gas is supplied from the fifth tank (705) and silane gas is supplied from the sixth tank (706) at an output pressure of IKg/Cm.
2, the first, second, fifth, and sixth flow controllers (71
3,714, 717, and 718). At the same time, the fourth control valve (710) is released and the fourth tank (710) is released.
Diborane gas diluted to 1100 pp with hydrogen gas from 04) 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 180 sec, the germane gas flow rate to 8 sec, and the ammonia gas flow rate to 2 sec.
The flow rate of ecm1 silane gas is 101005e, and the flow rate of diporane gas diluted to 1100pp with hydrogen gas is 10.
105e to allow it 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, the conductive substrate (752) on which the a-C film is formed is heated to 240°C, and is heated at a frequency of 13.58 MHz from a high frequency power source (739) while the gas flow rate and pressure are stable. Power application '21FM (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=si film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Miba Seisakusho), Auger analysis, and IM.
When A analysis was performed, the hydrogen atoms contained were 21 atomic% and the boron atoms were 11 atomic ppm% of the total constituent atoms.
Nitrogen atoms are 0.3 at%, germanium atoms are 13.2
It was 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 at positive WI charging are shown in parentheses, but the highest charging potential is -600V (+600V), 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 570 V/.mu.m (590 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance. Also, in the dark from Vmax to Vmax 90
The time required for the dark decay to reach a surface potential of approximately 37%
seconds (approximately 38 seconds), and from this it was understood that it had sufficient charge retention performance. After initial charging to the highest charging potential, white light is used to brighten the surface potential to 20% of the highest charging potential. 11', the amount of light required was 1.5 lux·sec (1.4 lux·sec), 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 8.6erg/am2. (9,8erg/c
m2), and from this it was concluded 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.

Daishiden 4 Using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Fourth control valve (7
07, 708, 709, and 710), hydrogen gas from the first tank (701), butadiene gas from the second tank (702), ammonia gas from the third tank (703), and ammonia gas from the fourth tank (704). Carbon tetrafluoride gas was flowed into the first, second, third, and fourth flow controllers (713, 714, 715, and 716) each under an output pressure of 1.0 Kg/am2. Then, the scales of each flow rate 111M meter were adjusted to set the hydrogen gas flow rate to 120 sec and the butadiene gas flow rate to 60 sec.

The flow rate of ammonia gas was set to 6 sec, and the flow rate of carbon tetrafluoride gas was set to 160 sec, and the gas flowed into the reaction chamber (733) from the main pipe (732) via an intermediate mixer (731).

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 of 0x width 50x 3mm thick, heat it in advance to 120t', and with the gas flow rate and pressure stable, connect the low frequency amount m (741) with the connection selection switch (744) in advance. ) and apply 140W of power to the 4-pole (736) at a frequency of 5.
A plasma polymerization reaction was carried out for about 1 hour and 20 minutes by applying a frequency of 60 KHz, and a thickness of 15 μm was formed on the conductive substrate (752).
The a-C film was formed as a charge transport layer. After completing the film formation, stop applying power, close the control valve, and open the reaction chamber (733).
The inside was thoroughly evacuated.

Organic elemental analysis was performed on the a-CI 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. The amount of O atom %, roughly, the amount of nitrogen atoms was 2.4 atom % based on the total constituent atoms.

11t load generation layer formation 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, hydrogen gas is released from the first tank (701), germane gas is removed from the second tank (702),
Nitrogen gas from the fifth tank (705) and the sixth tank (
706) to the first, second, fifth, and sixth flow rate controllers (713, 7) under an output pressure of IKg/am2.
14, 717, and 718). at the same time,
Release the fourth control valve (710) and release the fourth tank (704).
Diborane gas diluted to 1100 pp with hydrogen gas is passed through the fourth flow rate controller (
716).

Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200.
secm, the flow rate of nitrogen gas is 10s105e, the flow rate of germane gas is 10105e, the flow rate of silane gas is 1010
05e, the flow rate of diborane gas diluted to 1100pp with hydrogen gas was set to 50sec, and the reaction chamber (733)
Don't let it flow inside.

After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 0.8 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 250°C, and is heated to 13.56 MH2 from a high frequency power source (739) under a stable gas flow rate and pressure. A power of 40 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 ON H analysis in metal (EMGΔ-1300 manufactured by Miba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 24 at.% of the total constituent atoms, and the hydrogen atoms were at 45 at.ppm.
, nitrogen atoms are 1.0 at%, germanium atoms are 15.
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 at the time of positive charging are shown in parentheses, and the highest charging potential is -330V (+310V), 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 22 V/.mu.m (20 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).
From this, it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using white light, and the amount of light required was 3. Flux・
seconds (3°4 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.

Example 5 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 71"0), hydrogen gas from the first tank (701), butadiene gas from the second tank (702), nitrogen 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 scales of each flow rate controller to set the hydrogen gas flow rate to 180 seconds cm, the butadiene gas flow rate to 40 seconds, and the nitrogen gas flow rate to 7 seconds.
ms and the flow rate of carbon tetrafluoride gas to be 10105e, the main pipe (
732) into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 2.0.
The pressure control valve (745) was adjusted so that the pressure was Torr. On the other hand, as a conductive substrate (752), 50 fir x 5 horizontal
Using an aluminum substrate of 0 x 3 mm thickness, 180
℃, 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).
In 6), a plasma polymerization reaction was performed for about 30 minutes by applying a power of 200 Watts at a frequency of 400 KHz, and an a-C film with a thickness of 15 μm was formed as a charge transport layer on a conductive substrate (752). After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms that could be contained was 40 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 nitrogen 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 second control valve (708), the third control valve (709), the fifth control valve (711), and the 6F1 node valve (712) are released, and hydrogen gas is transferred from the first tank (701) to the second tank ( 7
germane gas from 02), tetrafluorosilane gas from the third tank (703), nitrogen gas from the fifth tank (705),
and silane gas from the sixth tank (706) at an output pressure of I
1st, 2nd, 3rd, 5th, and 6th under Kg/cm2
Flow controller (713, 714, 715, 717, and 7
18) It was allowed to flow into the interior. At the same time, the fourth control valve (710)
100 with hydrogen gas from the fourth tank (704).
Diborane gas diluted to ppm is supplied at 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 set the hydrogen gas flow rate to 200 scCm and the germane gas flow rate to 6 seconds.
, the flow rate of silane tetrafluoride gas was 503 CCm s, the flow rate of nitrogen gas was 1 sccm, and the flow rate of silane gas was 50 sec.
The flow rate of diborane gas diluted to 1100pp with m1 hydrogen gas was set to 101005e, and the reaction chamber (
733). After each flow rate stabilizes,
The pressure regulating valve (745) was adjusted so that the pressure inside 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. Power application [t! (736) was applied with a power of 35 Watts to generate a glow discharge. Do this discharge for 5 minutes,
A charge generation layer with a thickness of 0.3 μm was obtained.

The obtained a-3i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Miba Seisakusho), Auger analysis, and I
According to MA analysis, the hydrogen atoms that can be contained are 22 at% of the total constituent atoms, and the boron atoms are 95 at.ppm.
, 5 at% of fluorine atoms, 0.1 at% of nitrogen atoms, and 10.3 at% of germanium 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 charging potential is -630V (+700V), 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 41 V/.mu.m (46 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 13 seconds (approximately 12 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness decay was performed using white light until the surface potential reached 20% of the highest charging potential. 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. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Procedural amendment October 21, 1988 Director General of the Patent Office Kunio Ogawa 2. Title of invention Photoreceptor 3. Case of the person making the amendment Relationship with Applicant address 2-30 Azuchi-cho, Higashi-ku, Osaka Osaka Kokusai Building name (607) Mi/Ruta Camera Co., Ltd. Voluntary amendment 5, drawing subject to amendment 6, content of amendment Drawing 8 was changed to "Corrected drawing 8" ” will be corrected.

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; A hydrogenated amorphous silicon germanium film containing nitrogen atoms and at least one of phosphorus atoms and boron atoms, or a fluorinated amorphous film containing nitrogen atoms and at least one of phosphorus atoms and boron atoms. A photoreceptor characterized by having a silicon germanium film.