JPS6381486A - 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. oxygen atoms and halogen atoms to form an electric charge transfer layer and using a hydrogenated or fluorinated amorphous silicon germanium film 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 oxygen 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 atom 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 Field of the Invention The present invention relates to a photoreceptor having a charge generation layer and a charge transport layer.

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

The main electrophotographic photoreceptor materials conventionally used include inorganic substances such as amorphous selenium, selenium arsenide, selenium telluride, cadmium sulfide, zinc oxide, amorphous silicon, polyvinyl carbazole, metal phthalocyanine,
Examples include organic substances such as disazo pigments, trisazo pigments, perylene pigments, triphenylmethane compounds, triphenylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, oxazole compounds, and oxadiazole compounds. In addition, the configurations include a single-layer structure in which these substances are used alone, a binder-type structure in which they are dispersed in a binding material, 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 gas silicon mentioned above, have unfavorable properties. In addition, in order for an electrophotographic photoreceptor to be actually used in a copying machine, it must always maintain stable performance even when exposed to harsh environmental conditions such as charging, exposure, development, transfer, neutralization, and cleaning. However, all of the organic substances mentioned above have poor durability and many unstable factors in terms of performance.

In order to eliminate such drawbacks, in recent years, amorphous silicon produced by a glow discharge method has been increasingly applied to electrophotographic photoreceptors as a material with improved toxicity and high durability. However, while amorphous silicon requires a large amount of silane gas as a raw material, it is an expensive gas, so the resulting electrophotographic photoreceptor is also significantly more expensive than a conventional photoreceptor. In addition, there are many inconveniences in production, such as the slow film formation rate and the generation of explosive silane undecomposed products in the form of dust as the film formation time increases. Furthermore, if this dust gets mixed into the photosensitive layer during manufacturing, it will have a significant negative effect on image quality. Generally, amorphous silicon has low charging performance due to its high specific dielectric constant, 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 Applied 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 Pol
ymerization), its film formability has been discussed.

However, plasma organic polymer films prepared by conventional methods are used only for applications that assume insulation properties, that is, they are considered to be insulating films with a specific resistance of about <1016 Ωcm, like ordinary polyethylene films. Or, it was used based on the recognition that it was such a film.In actual use for electrophotographic photoreceptors, from the same recognition, protective layers, adhesive layers, blocking layers, or It has been limited to 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.

In addition, 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 formed as a protective layer on the surface of a polyvinylcarbazole-selenium photoreceptor.
A photoreceptor is disclosed. Japanese Patent Publication No. 59-214
Japanese Patent No. 859 discloses a technique for forming a protective layer on the surface of an amorphous silicon photoreceptor by plasma polymerizing an organic hydrocarbon monomer such as styrene or acetylene to form a film of about 5 μm. JP-A No. 60-61761 discloses a photoreceptor provided with a diamond-like carbon thin film of 500 to 2 μm as a surface protective layer, and it is said that the film thickness is preferably 2 μm or less in terms of light transmission. ing.

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

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

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

On the other hand, regarding the amorphous silicon film, Spear (W
, E, 5pear) and 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 it is a material whose polarity can be controlled, attempts have been made to apply it 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.

As mentioned above, the 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. This film is not necessary 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 oxygen 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. Although the theoretical interpretation has many unclear points even for the present inventors, it is not possible to discuss it in detail. Hydrogenated or Since the band structure formed by the fluorinated amorphous silicon germanium film has a similar energy level in the conduction band or valence band, hydrogenation containing at least one of phosphorus atoms and boron atoms as well as nitrogen atoms is possible. Alternatively, carriers generated in the fluorinated amorphous silicon germanium film are easily injected into the hydrogenated amorphous carbon film containing oxygen atoms and halogen atoms, and furthermore, these carriers are absorbed by the relatively unstable energy described above. It is presumed that this is because the hydrogenated amorphous carbon film containing oxygen atoms and halogen atoms can travel suitably through the action of state 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 oxygen A hydrogenated amorphous carbon film containing atoms and halogen atoms is used as a charge transport layer, and hydrogenated or fluorine containing at least one of phosphorus atoms and boron atoms as well as nitrogen atoms. An object of the present invention is to provide a photoreceptor using an R4 film of amorphous silicon germanium as a charge generation layer.

In other words, the present invention provides a function-separated photoreceptor having a charge generation layer and a charge transport layer, in which the charge transport layer has at least oxygen atoms generated from a plasma polymerization reaction. A hydrogenated amorphous carbon film containing a halogen atom, and a hydrogenated or fluorinated amorphous carbon film containing at least one of a phosphorus atom and a boron atom as well as a nitrogen atom. Regarding a photoreceptor characterized in that it is a silicon germanium film (hereinafter, the charge transport layer according to the present invention is an a-C film and the charge generation layer is an a-Si germanium 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 requires only charge transport ability even if it does not have charge generation ability. This was done to solve these problems.

That is, the present invention provides a hydrogenated amorphous carbon film containing at least oxygen atoms and halogen atoms generated by glow discharge as a charge transport layer, and a hydrogenated amorphous carbon film containing at least oxygen atoms and halogen atoms generated by glow discharge as a charge generation layer. 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 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 good charging ability, durability, and weather resistance. It has excellent electrophotographic photoreceptor performance such as durability and environmental pollution resistance, and is also excellent in light transmission, so it can provide an extremely high degree of freedom when forming a laminated structure as a functionally separated photoreceptor. It is. In addition, the charge generation layer has excellent photoconductivity for visible light or light with a wavelength near semiconductor laser light, and has an extremely thin film thickness compared to conventional amorphous silicon photoreceptors. It is something that can be put to good use.

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

The phase state of the hydrocarbon does not necessarily have to be a gas phase at room temperature and normal pressure, but may be a liquid phase as long as it can be vaporized through heating, reduced pressure, etc. (melting, evaporation, sublimation, etc.). A solid phase can also be used.

There are many types of hydrocarbons that can be used), but examples of saturated hydrocarbons include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane,
Decane, undecane, dodecane, tritecane, tetradecane, pentadecane, hexacosane, hebutatecane, octacosane, nonadecane, eicosane, heneicosane, tocosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, todoriacontane, pentacosane Normal ti rough ins such as triacontane, 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-)dimethylpentane, 2,3°3-trimethylpentane, 2,3.4-trimethylpentane, isonanone, and other isoparaffins. 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,
Olefins such as 1-nonene, 1-decene, diolefins such as allene, methylalene, butadiene, pentadiene, hexadiene, cyclopentadiene, and triolefins such as ocimene, allocimene, myrcene, hexatriene, Also, acetylene, butadiine, 1.゛3-pentadiyne, 2,4-hexadiyne, methylacetylene, 1-butyne, 2-butyne, 1-
Benzene, 1-hexyne, 1-heptyne, 1-octyne, 1-nonine, 1-decyne, etc. are used.

Examples of alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, Cycloparaffins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, and cycloolefins such as limonene, tervirun, phelandrene, sylvestrene, thuene, carene, pinene, bornylene, kamphuen, fuenchen , cycloundecane, tricyclene, bisabolene, zingiberene, curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, campholene, phylloclatene, bodocarbrene, mirene, and other terpenes, steroids, and the like are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, 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 .mu.m, especially 7 to 20 .mu.m, is suitable; if it is thinner than 5 .mu.m, the charged potential will be low, making it impossible to obtain a sufficient density of the copied image. Moreover, if it is thicker than 50 μm, it is not preferable in terms of productivity.

This a-CM 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 transported without being trapped and contribute to bright attenuation. is possible.

The process of forming a-CPI from a raw material gas in the present invention includes a method in which the raw material gas undergoes a plasma state generated by a plasma method using direct current, low frequency, high frequency, microwave, etc. Although it is most preferred, it may also be formed through an ion state generated by ionization vaporization method, ion beam vaporization method, etc.
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 of these.

In the present invention, in addition to hydrocarbons, oxygen compounds are used to add at least oxygen atoms into the a-C film. The phase state of the oxygen compound does not necessarily have to be a gas phase at room temperature and normal pressure; it can be used in either a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It is. Examples of oxygen compounds include oxygen, ozone, water vapor, -carbon oxide, carbon dioxide, carbon suboxide, and other inorganic compounds, hydroxyl groups (-OH),
Aldehyde group (-COH), 7)tt group (RCO-
, -CRO), ketone group (>Co), ether bond (
Organic compounds having functional groups or bonds such as -0-), ester bonds (-Coo-), and oxygen-containing heterocycles are used. As the organic compound having a hydroxyl group, for example, methanol, ethanol, propatool, butanol, furyl alcohol, fluoroethanol, fluorobutanol, phenol, cyclohexanol, benzyl alcohol, furfuryl alcohol, etc. are used. Examples of organic compounds having an aldehyde group include:
Formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, acrolein, benzaldehyde, furfural, etc. are used. Examples of organic compounds having an acyl group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, palmitic acid,
Stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, toluic acid, salicylic acid, cinnamic acid,
Naphthoic acid, phthalic acid, furanic acid, etc. are used. Examples of organic compounds having a ketone group include a7tone, ethyl methyl ketone, methyl propyl ketone, butyl methyl ketone, binacolon, diethyl ketone, methyl vinyl ketone, mesityl oxide, methyl heptenone, cyclobutanone, cyclopentanone, cyclohexanone,
Acetophenone, propiophenone, butyrophenone,
Parellofoenone, dibenzyl ketone, acetonaphthone,
Acetochenone, acetofuron, etc. are used. Examples of organic compounds having an ether bond include methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, ethyl methyl ether, methyl propyl ether, methyl butyl ether, methyl amyl ether, ethyl propyl ether, ethyl butyl ether, and ethyl amyl ether. , vinyl ether,
Allyl ether, methyl vinyl ether, methyl furyl ether, ethyl vinyl ether, ethyl furyl ether, anisole, phenetol, phenyl ether, benzyl ether, phenylbenzyl ether, naphthyl ether, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydrobilane, dioxane, etc. are used. Examples of organic compounds having an ester bond include methyl formate, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl propionate, ethyl propionate, and propion. propyl acid, butyl propionate, amyl propionate,
Methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate,
Amyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, amyl valerate, methyl benzoate,
Ethyl benzoate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, methyl salicylate, ethyl salicylate, propyl salicylate, butyl salicylate, amyl salicylate, methyl anthranilate, ethyl anthranilate, butyl anthranilate, amyl anthranilate, Methyl phthalate, ethyl phthalate, butyl phthalate, etc. are used. Examples of heterocyclic compounds containing oxygen include furan,
Oxazole, furazane, biran, oxazine, morpholine, benzofuran, pandioxazole, chromene,
Chroman, dibenzofuran, xanthine, phenoxazine, oxolane, dioquinrane, oxathiolane, oxadiazine, benzisoxazole, etc. are used.

In the present invention, the amount of oxygen atoms contained as a chemical modifier is 7.0 at % or less based on all constituent atoms. Here, the content of oxygen atoms in the film can be determined by a conventional method of elemental analysis, such as Auger analysis. When the amount of oxygen atoms is higher than 7.0 at%, the oxygen atoms, which had ensured suitable transport properties when added in small amounts, conversely exhibit the effect of lowering the resistance of the film, resulting in a decrease in charging ability. will come. In addition, some oxygen source gases, such as oxygen gas, ozone gas,
- Carbon oxide gas has a strong etching effect, and if you try to increase the amount of oxygen atoms added to the film by increasing the flow rate, the film formation rate will decrease and a certain film thickness will be required. This is inconvenient when forming a 1i cargo transport layer. Therefore, the range of the amount of oxygen atoms added in the present invention is important.

In the present invention, the amount of oxygen atoms contained as a chemical modifier can be controlled mainly by increasing or decreasing the amount of the aforementioned oxygen compound introduced into the reaction chamber in which the plasma reaction is performed. If the amount of oxygen compound introduced is increased,
The amount of oxygen atoms added to the a-C film according to the present invention is increased (
On the other hand, if the amount of oxygen compounds introduced can be reduced, it is possible to reduce the amount of oxygen atoms added to the a-C film according to the present invention.

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 a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It is. Examples of halogen compounds include fluorine,
Inorganic compounds such as chlorine, bromine, iodine, hydrogen fluoride, chlorine fluoride, bromine fluoride, iodine fluoride, hydrogen chloride, bromine chloride, iodine chloride, hydrogen bromide, iodine bromide, hydrogen iodide, etc., and halogenated Organic compounds such as alkyl, halogenated aryl, halogenated styrene, halogenated polymethylene, and haloform 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 heptyl, hebutyl chloride,
Hebutyl bromide, hebutyl iodide, octyl fluoride, octyl chloride, octyl bromide, octyl iodide, nonyl fluoride, nonyl chloride, nonyl bromide, nonyl iodide, decyl fluoride, decyl chloride, decyl bromide, Decyl iodide, etc. are used. As the aryl halide, for example, fluorobenzene, chlorobenzene, brombenzene, iodobenzene, chlorotoluene, bromotoluene, chlornaphthalene, bromnaphthalene, etc. are used. As the halogenated styrene, for example, chlorstyrene, bromustyrene, iodostyrene, fluorostyrene, etc. are used. Examples of halogenated polymethylene include methylene chloride, methylene bromide, methylene iodide, ethylene chloride, ethylene bromide, ethylene iodide, trimethylene chloride, trimethylene bromide, trimethylene iodide, butane dichloride, butane dibromide, Butane dichloride, pentane dichloride, pentane dibromide, pentane dichloride, hexane dichloride, hexane dibromide, hexane dichloride, hexane dichloride, hebutane dibromide, hebutane dichloride, octane dichloride , octane dibromide, octane shoide, 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 is not guaranteed.If the amount of halogen atoms is higher than 25 at%, the halogen atoms, which would have guaranteed suitable charge transport properties and prevention of residual potential generation when added in an appropriate amount, On the contrary, it has the effect of lowering the charging ability, or even lowering the dark resistance after aging, leading to a decrease in the charge retention ability during storage for several months.Furthermore, film formation properties are not necessarily guaranteed, and the film's This results in peeling, oily formation, or pulverization. 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 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, 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-Si film in the present invention is preferably 30 at % or less with respect to the total of silicon atoms and germanium atoms. Here, the contents of germanium atoms and silicon atoms can be determined by a conventional method of elemental analysis, for example, Auger analysis. The content of germanium atoms can be increased by increasing the flow rate of germane gas flowing during film formation. As the content of germanium atoms increases, the long wavelength sensitivity of the photoreceptor of the present invention improves, and 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 contained in the a-3i film in the present invention is important.

In the present invention, the amount of phosphorus atoms or phosphorus atoms contained as chemical modifiers 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 2oO00 atomic 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 FIA elementary 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 electric resistance value of the a-3i film becomes low, making it difficult for the a-Si film to be subjected to electric fields due to corona charging, etc., and photoexcited carriers are Efficiency <a-(4M will not be injected, resulting in a decrease in sensitivity. Also, charging ability will also decrease. If the content of nitrogen atoms in the film is higher than 3 at%, it is suitable for adding a small amount of nitrogen atoms. Nitrogen atoms, which guarantee a good charging ability, increase the resistance of the a-3i film and reduce the mobility of charges when added in excess, resulting in a decrease in sensitivity.Therefore, the amount of nitrogen atoms added in the present invention is Range 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-3i film as the charge generation layer in the present invention is 0.1 to 5 μm for use in a normal electrophotographic process, and if it is thinner than 0.1 μm, light absorption is insufficient. As a result, sufficient charge generation is not performed, resulting in a decrease in sensitivity. Moreover, if it is thicker than 5 μm, it is not preferable in terms of productivity. This a-Si film has a rich charge generation ability,
In general, in the laminated structure with the a-C film, which is the most characteristic feature of the present invention, generated carriers can be efficiently injected into the a-C film, contributing to suitable bright attenuation.

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

In the present invention, the amount of nitrogen atoms, phosphorus atoms, or boron atoms contained as chemical modifiers is mainly determined by the amount of 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 of introduced. By increasing the amount of nitrogen compound gas, phosphine gas, or diborane gas introduced, it is possible to increase the amount of nitrogen atoms, phosphorus atoms, or boron atoms added to a-3illiJ according to the present invention. On the other hand, if the amount of nitrogen compound gas, phosphine gas, or diborane gas introduced is reduced, a-
It is possible to reduce the amount of nitrogen atoms, phosphorus atoms, or boron atoms added to 3iFJ.

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

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

When the surface of the photoreceptor is used by imagewise exposure after being positively charged, for example, with a corona band 7!1 device, in FIG. 1, the holes generated in the charge generation layer (3) are
), 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 toward the photoreceptor surface, 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-3i film with poor halide properties, it is often 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-5I film, which ensures adhesiveness and injection blocking effect in most cases. It is preferable to provide an intermediate layer for this purpose. In the case of the configurations shown in FIGS. 1 and 3, since the bonding surface with the conductive substrate is the charge transport layer according to the present invention, which has excellent adhesiveness and injection blocking effect, it is not necessary to provide an intermediate layer. For example, an intermediate layer may be provided for the purpose of adjusting compatibility with a manufacturing process before forming a photosensitive layer, such as a pretreatment method for a conductive substrate.

FIG. 6 shows, as a further embodiment, 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. a-CI'A according to the invention may also be used. however,
For example, when the material used is an insulating material as described in the conventional example, the film thickness should be 5 μm to prevent the generation of residual potential.
It must be kept below.

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

FIG. 7 shows a photoconductor manufacturing apparatus according to the present invention, and in the figure (701) to (706) are first to sixth tanks in which the raw material compound and carrier gas, which are in a gas phase at room temperature, are sealed, respectively. The tanks are the first to sixth control valves (707)
〜(712) and the first to sixth flow rate controllers (713)〜(
718) is not connected. (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 control valves (mW).
728) to (730). These gases are mixed in a mixer (731) and then passed through the main pipe (732).
) into the reaction chamber (733). 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 (73?). A high frequency power matching device (738) is connected to the power application electrode (736).
High frequency power supply (739), matching box for low frequency power (
740) via low frequency type! (741), a DC power source (743) is connected via a low-pass filter (742), and power with different frequencies can be applied by a connection selection switch (744). Reaction chamber (733
) can be adjusted by a pressure control valve (745), and the pressure in the reaction chamber (733) can be reduced by an exhaust system selection valve (74).
6) via a diffusion pump (747), an oil rotary pump (748), or a cooling exclusion device ffi (749).
, a mechanical booster pump (750), and 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,
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. The reaction chamber (733) is also heated M(
751), and a conductive substrate (752) is installed on the electrode arranged inside. In FIG. 7, the conductive substrate (752) is fixed to the ground electrode (735), but it may also be fixed to the power application electrode (736), or it may be arranged roughly on both sides. Good too.

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 can be installed inside, and an electrode heater (837) is arranged inside. Conductive substrate (
852) There is also a cylindrical power application electrode (
836) is arranged, and a 1tw1 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, the electrode heater and the conductive substrate fixedly disposed on the electrode are heated to a predetermined temperature. If necessary, an undercoat layer or a charge generation layer may be provided in advance on the conductive substrate in order to obtain a desired photoreceptor structure from among those described above. The present apparatus or a separate apparatus may be used to provide the undercoat layer or the charge generation layer. Next, the raw material gases are introduced into the reaction chamber from the first to sixth tanks and the first to third containers while being kept at a constant flow rate using the first to ninth flow rate controllers, and the inside of the reaction chamber is kept constant using the pressure control valve. Maintain a reduced pressure. After the gas flow rate is stabilized, a connection selection switch is used to select, for example, a high frequency power source, and high frequency power is applied to the power application electrode.

A discharge is started between both molds w3, 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 explained below with reference to Examples.

By using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were 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 Hif 10), hydrogen gas from the first tank (701), acetylene gas from the second tank (702), oxygen gas from the third tank (703), and fourth tank (704). The first, second, third, and fourth flow rate controllers (713, 714, 715, and 716) each output carbon tetrafluoride gas under an output pressure of 1.0 Kg/cm2.
It flowed inside. Then, by adjusting the scale of each flow rate controller, set the flow rate of hydrogen gas to 180 seconds, the flow rate of acetylene gas to 40 seconds, the flow rate of oxygen gas to 4 seconds, and the flow rate of carbon tetrafluoride gas to 10105e. Through the mixer (731), the main pipe (732
) into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) decreases to 2. ○Tor
The pressure regulating valve (745) was adjusted so that the temperature was r. On the other hand, as the conductive substrate (752),! Using an aluminum substrate of 50 x 50 x 3 mm thick, preheat it to 250°C, and with the gas flow rate and pressure stable, connect the high frequency power source (739) using the connection selection switch (744). A 200 Watt power was applied to the power application electrode (736) at a frequency of 13.56 MHz to perform a plasma polymerization reaction for about 3 hours, thereby forming an a-〇 film with a thickness of 15 μm on the conductive substrate (752). It 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 34 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, fluorine atoms, was 2.0 at% based on the total constituent atoms, and the amount of oxygen atoms was roughly 1.1 at% based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
The second control valve (708), the fifth W node valve (711), and the sixth control valve (712) are released, and the first tank (701) is opened.
Hydrogen gas from the second tank (702), nitrogen gas from the fifth tank (705), and silane gas from the sixth tank (706) are supplied to the first, second, and third tanks under an output pressure of IKg/cm2. 5, and a sixth flow rate controller (713,
714, 717, and 718). At the same time, the fourth control valve (710) is released and the fourth tank (704
) Diborane gas diluted to 1100 pp with hydrogen gas was flowed into the fourth flow rate controller (716) under an output pressure of 1.5 Kg/cm2.

Adjust the mW scale on each flow rate side to set the hydrogen gas flow rate to 200.
secm1 germane gas flow rate 6 sccm.

The flow rate of nitrogen gas was set to 0.01 sec, 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 1105 CC, 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 has been formed is heated to 250°C, and while the gas flow rate and pressure are stable, a high frequency power source (739) is applied to the conductive substrate (752) at a frequency of 13.56.
Power applied under MHz 35W to 8III (736)
A glow discharge was generated by applying a power of tt. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-St film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Miba Seisakusho), Auger analysis, and IM.
When A analysis was conducted, the hydrogen atoms contained were 23 at% of the total constituent atoms, and the boron atoms were 10 at ppm5.
Nitrogen atoms are 0.001 at%, germanium atoms are 11
It was atomic%.

Characteristics: When the obtained photoreceptor was used in a conventional Carlson process with both negative and positive charging, the following properties were obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -610V (+580V).In other words, since the total photoreceptor film thickness is 15°3μm, the charging ability per μm is 40V. /um (38V/μm), which was extremely high, and it was understood from this that it had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 20 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, and the amount of light required was 3.1 lux · seconds (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.

^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. Control valve (707,
709 and 710), and the first tank (701)
Hydrogen gas, oxygen gas from the third tank (703), and carbon tetrafluoride gas from the fourth tank (704) are controlled at the first, third, and fourth flow rates under an output pressure of 1.0 Kg/cm2, respectively. into the vessels (713, 715, and 716).

At the same time, styrene gas is supplied from the first container (719) to the first temperature controller (722) at a temperature of 35°C and to the seventh flow rate suppressor (7
28) Don't let it flow inside. Then, the scales of each flow rate limiter were adjusted to set the hydrogen gas flow rate to 60 seconds and the styrene gas flow rate to 30 seconds.

Set the flow rate of oxygen gas to 8 sec and the flow rate of carbon tetrafluoride gas to 30 sec, and mixer (
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
) is 950 X+! Using a 50 x 53 mm aluminum substrate, preheat it to 180°C, and with the gas flow rate and pressure stable, connect it to the low frequency power source (741) using the connection selection switch (744).
) and applied 200W to the power application electrode (736).
A plasma polymerization reaction was carried out for about 45 minutes by applying power at a frequency of 1120 KHz 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, stop applying power, close the control valve,
The inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 48 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, fluorine atoms, was 6.1 at% based on the total constituent atoms, and the amount of oxygen atoms was roughly 2.3 at% based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
2nd: Open the A section valve (708), the 5th control valve (711), and the 6th control valve (712), hydrogen gas from the first tank (701), Germanic gas 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/am.
2, the first, second, fifth, and sixth flow control devices (71
3,714, 717, and 718). At the same time, the fourth control valve (710) is released and the fourth tank (710) is released.
04) Diborane gas diluted to 1100pp with hydrogen gas is subjected to the fourth flow rate control under an output pressure of 1.5Kg/cm2! (716). 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 diborane gas diluted to 1100pp with hydrogen gas is 10.
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 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 when the gas flow rate and pressure are stable, the conductive substrate (752) is heated to a lower frequency of 13.56 MHz than the high frequency type 1 (739). 4 to the power application electrode (736) with
A power of 5 Watts was applied to generate glow discharge.

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

The obtained a-5i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 21 atomic % and the boron atoms were 11 atomic ppm based on the total constituent atoms.
, nitrogen atoms are 0.3 at%, germanium atoms are 13.
It was 2 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 -610V (+580V).In other words, since the total photoreceptor film thickness is 15°3μm, the charging ability per μm is 40V. /μm (38V/μm), which is extremely high, and it can be understood from this that it has sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 14 seconds (approximately 13 seconds).
seconds), and from this we can understand that it has sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using white light.The amount of light required was 2.3 lux·sec (1.2 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. Valve (707,
709 and 710), and the first tank (701)
Hydrogen gas, oxygen gas from the third tank (703), and carbon tetrafluoride gas from the fourth tank (704) are controlled at the first, third, and fourth flow rates under an output pressure of 1 and OKg/cm2, respectively. The liquid flowed into the vessels (713, 715, and 716).

At the same time, styrene gas is supplied from the first container (719) to the seventh flow rate controller (722) at a temperature of 35°C.
28) It was allowed to flow into the interior. The scales of each flow rate controller were adjusted to set the hydrogen gas flow rate to 603 CCm and the styrene gas flow rate to 30 seconds.

Set the flow rate of oxygen gas to 8 sec1 and the flow rate of carbon tetrafluoride gas to 30 sec, and mixer (
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°○Torr. On the other hand, a conductive substrate (752
), use an aluminum substrate measuring 50 mm wide x 3 mm thick, heat it to 180°C in advance, and with the gas flow rate and pressure stable, connect the connection selection switch (7
44), the low frequency power source (741) connected to the conductive substrate ( 752) Thickness 1 on top
A 5 μm a-C film was formed as a charge transport layer. After film formation is complete, stop applying power, close the control valve, and close the reaction chamber (
733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms that could be contained was 48 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, fluorine atoms, was 6.1 atomic % based on the total constituent atoms, and the amount of oxygen atoms was roughly 2.3 atomic % based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
The second control valve (708), the fifth control valve (711), and the sixth: A section valve (712) are released, and the first tank (701) is opened.
hydrogen gas from the second tank (702), germane gas from the second tank (702), nitrogen gas from the fifth tank (705), and silane gas from the sixth tank (706). 5, and a sixth flow rate controller (713,
714, 717, and 718). At the same time, the fourth control valve (710) is released and the fourth tank (704
) diborane gas diluted to 1100 pp with hydrogen gas was allowed to flow 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, and the flow rate of nitrogen gas is 10105e.

The flow rate of germane gas was set to 10105e, the flow rate of silane gas was set to 101005e, and the flow rate of diborane gas diluted to 10 oppm with hydrogen gas was set to 50 seconds, and these were flowed into the reaction chamber (733).

After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 0.8 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 250°C, and is heated 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 ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 24 at% of the total constituent atoms, and the boron atoms were 45 at pI'
mN 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 during positive charging are shown in parentheses, and the highest charging potential is -660V (+680V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 43 V/.mu.m (44 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 15 seconds (approximately 17
seconds), and from this it was understood that it had sufficient charge retention performance. 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 (1.2 lux・seconds), and from this it was understood that it had sufficient photosensitivity performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using semiconductor laser light (emission wavelength 780 nm), and the amount of light required was 10. O
erg/am2 (7.3 erg/cm2), and from this it was understood that it had sufficient long wavelength light sensitivity performance.

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

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

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

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Fourth control valve (7
07, 708, 709, and 710), hydrogen gas from the first tank (701), butadiene gas from the second tank (702), carbon dioxide gas from the third tank (703), and fourth tank (704). Carbon tetrafluoride gas was then flowed into the first, second, third, and fourth flow rate controllers (713, 714, 715, and 716) under an output pressure of 1.0 Kg/am2, respectively. Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 60scam, the butadiene gas flow rate to 60sec, the carbon dioxide gas flow rate to 12sec, and the carbon tetrafluoride gas flow rate to 160sec.
Set it so that it is cm, and mix it in the middle! (731) and flowed into the reaction chamber (733) from the main pipe (732).

After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 1.6 Torr. On the other hand, as the conductive substrate (752), fir 5
Using an aluminum substrate of 0 x width 50 x thickness 3 mm, it was preheated to 120°C, and with the gas flow rate and pressure stable, it was connected to the low frequency power source (741) using the connection selection switch (744). ) and apply 130W of power to the power application electrode (736) at a frequency of 500K.
Plasma polymerization reaction was carried out under Hz for about 1.5 hours to form a 15 μm thick a-C film as a charge transport layer on the conductive substrate (752).

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

Organic elemental analysis was performed on the a-C film obtained as described above, and it was found that the amount of hydrogen atoms contained was 51 atomic% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, fluorine atoms, contained was 21.0 at % based on the total constituent atoms, and the amount of oxygen atoms was roughly 2.0 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),
releasing the second control valve (708), the third control valve (709), 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), nitrogen gas from the fifth tank (705), and silane gas from the sixth tank (706), at an output pressure of IK.
g/cm2 under the first, second, third, fifth, and sixth flow controllers (713, 714, 715, 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.
am2 into the fourth flow controller (716). Adjust the scale of each flow rate controller to increase the hydrogen gas flow rate to 2.
00 sccm, and the flow rate of germane gas was 6 sc Cm.
sThe flow rate of silane tetrafluoride gas is 50 sec1, the flow rate of nitrogen gas is 1 secm, the flow rate of silane gas is 50 sec1
The flow rate of diborane gas diluted to 1100pp with hydrogen gas was set to 101005e, and the reaction chamber (73
3) It was allowed to flow into the interior. After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure 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. A power of 35 Watts was applied to the power application electrode (736) to generate glow discharge. This discharge was performed for 5 minutes, and the thickness was 0.
．． A charge generation layer of 3 μm was obtained.

The obtained a-3i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When performing MA analysis, it was found that the hydrogen atoms contained were 22 at % of the total constituent atoms, and the boron atoms were 95 at ppm.
The content of fluorine atoms was 5 at%, the content of nitrogen atoms was 0.1 at%, and the content of germanium atoms was 10.3 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 extremely high at 21 .mu./.mu.m (22 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

Also, the time required for dark decay from Vmax to 90% of the surface potential of Vmax in the dark is approximately 4 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.The required scene was 4.3 lux.
seconds (3°1 lux·sec), and from this it was understood that it had sufficient photosensitivity performance.

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

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

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

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Control valve (707
, 708, 709, and 710), hydrogen gas from the first tank (701), butadiene gas from the second tank (702), oxygen gas from the third tank (703), and hydrogen gas from the fourth tank (704). First, second, third, and fourth flow rate controllers (713, 714, 715, and 716) each supplying fluorocarbon gas under an output pressure of 1.0 Kg/am2.
It flowed inside. Then, by adjusting the scale of each flow rate controller, set the flow rate of hydrogen gas to 180 seconds, the flow rate of butadiene gas to 40 seconds, the flow rate of oxygen gas to 4 seconds, and the flow rate of carbon tetrafluoride gas to 10105e, and mix in the middle. through the main pipe (732)
) into the reaction chamber (733). After each flow rate stabilized, the pressure inside the reaction chamber (733) reached 2.0 Torr.
The pressure regulating valve (745) was adjusted so that the temperature was r. On the other hand, as the conductive substrate (752), an aluminum substrate of 50 x 50 x 3 mm thick is used, heated to 180°C in advance, and when the gas flow rate and pressure are stable, connect the connection selection switch (744). The low-frequency power source (741) connected to the conductive substrate (752) is turned on, and 200 Watt power is applied to the power application electrode (736) at a frequency of 400 KHz to perform a plasma polymerization reaction for about 30 minutes. An a-C film having a thickness of 15 μm was formed thereon as a charge transport layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on a C1l'j- obtained as 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, ie, fluorine atoms, was 4.1 at% based on the total constituent atoms, and the amount of oxygen atoms was roughly 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 (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).
The phosphine gas diluted to 10 ppm with hydrogen gas is passed through the fourth flow rate controller (
716).

Adjust the scale of each flow rate regulator to set the hydrogen gas flow rate to 200.
sec, the flow rate of germane gas is 6 sec, the flow rate of nitrogen gas is 3 sec, the flow rate of silane gas is 200 sec.
The flow rate of phosphine gas diluted to 1100 ppm with hydrogen gas was set to 1105 cc, and the flow rate 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 0.9 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 250°C, and 1ff of gas is heated.
When the l and pressure are stable, apply power type 1 (73
6), a power of 35 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 Itaba Seisakusho), audio analysis, and I
According to MA analysis, the hydrogen atoms that can be contained are 18 at% of all constituent atoms, the phosphorus atoms are 12 at ppm,
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 -500V (+770V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 33 V/.mu.m (50 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 12 seconds (approximately 19
seconds), and from this it was understood that it had sufficient charge retention performance. Furthermore, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential, and the amount of light required was 2.1 lux · seconds (6.9 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 4 Figure 6 Procedural amendment October 21, 1986

Claims (1)

[Claims] In a functionally separated photoreceptor having a charge generation layer and a charge transport layer, the charge transport layer is a hydrogenated amorphous carbon film containing at least oxygen atoms and halogen atoms; 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.