JPS6382460A - Photosensitive body - Google Patents

Abstract

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

Description

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

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, conventionally used electrophotographic photoreceptor materials each have their own drawbacks. One of these is their toxicity to the human body, and all inorganic substances, except for the amorphous silicon mentioned above, have unfavorable properties. In addition, in order for an electrophotographic photoreceptor to be actually used in a copying machine, it must always maintain stable performance even when exposed to harsh environmental conditions such as charging, exposure, development, transfer, neutralization, and cleaning. However, the organic materials mentioned above all 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, amorphous carbon H'J itself has been known for a long time as a plasma organic polymer film, such as diene (M, 5hen) and bell (A, T).

Journal of Applied Polymer Science (Journa Be1l), published in 1973.
l of Applied P.

lymer 5science), Volume 17, pages 885 to 892, the same author also reported in the 1979 American Chemical Society that all organic compounds can be produced from gases.
Plasma Pol
ymerization), its film formability has been discussed.

However, plasma organic polymer films prepared by conventional methods are used only for applications that assume insulation properties, that is, they are considered to be insulating films with a specific resistance of about <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 on the polymer layer. ing. Japanese Patent Application Publication No. 5
Publication No. 9-38753 discloses that a high resistance plasma polymerized film of 1013 to 10 I5 Ωam 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 photosensitive material in which a carbon film of about 1 to 5 μm is formed on the surface of an aluminum substrate as a vibrator layer to prevent aluminum atoms from diffusing into an amorphous silicon layer provided on an aluminum substrate during light irradiation. My body is fully revealed. 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 um or less from the viewpoint of residual charge.

These disclosures are all inventions in which a so-called undercode layer is provided between the substrate and the amorphous silicon layer,
There is no disclosure regarding charge transport properties, and a-Si
However, it does not solve the above-mentioned essential problems.

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

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

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

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

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

Philosophical Magazine published in 1976 by Q, L6 (:omber)
Since it was reported on pages 935 to 949 of Vol. 33 of I Magazine that polarity can be controlled, attempts have been made to apply it to various photoelectric devices. Regarding application to photoreceptors, for example, Japanese Patent Application Laid-open No. 5
6-62254, JP 57-119356, JP 57-177147, JP 57-1
No. 19357, Japanese Patent Application Laid-open No. 177149/1983,
JP-A-57-119357, JP-A-57-177
146, JP 57-177148, JP 57-174448, JP 57-17444
Amorphous silicon photoreceptors containing carbon atoms are disclosed in Japanese Patent Application Laid-open No. 57-174450, etc., but all of them aim to adjust the photoconductivity of amorphous silicon with carbon atoms. Furthermore, amorphous silicon itself requires a thick film.

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 nitrogen atoms and halogen atoms. In some cases, VR with hydrogenated or fluorinated amorphous silicon germanium film
It has been found that IW has charge transport properties and easily begins to exhibit suitable electrophotographic properties. There are many unclear points in the theoretical interpretation, even for the present inventor, and we cannot discuss it in detail, but it is a relatively unstable hydrogenated amorphous carbon film that contains nitrogen atoms and halogen atoms. The band structure formed by electrons in certain energy states, such as π electrons, unpaired electrons, and residual free radicals, is
Because hydrogenated or fluorinated amorphous silicon germanium has similar energy levels in the conduction band or valence band to the band structure formed by the hydrogenated or fluorinated amorphous silicon germanium, carriers generated in the hydrogenated or fluorinated amorphous silicon germanium film can easily convert into nitrogen. The carriers are injected into the hydrogenated amorphous carbon film containing nitrogen atoms and halogen atoms, and the carriers are further injected into the hydrogenated amorphous carbon film containing nitrogen atoms and halogen atoms by the action of the electrons in the relatively unstable energy state mentioned above. It is presumed that this is because it can travel suitably through the amorphous carbon film.

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 It is an object of the present invention to provide a photoreceptor in which a hydrogenated amorphous carbon film containing atoms and halogen atoms is used as a charge transport layer, and a thin film of hydrogenated or fluorinated amorphous silicon germanium is used as a charge generation layer. purpose.

That is, the present invention provides a functionally separated photoreceptor having a charge generation layer and a charge transport layer, wherein the charge transport layer contains at least nitrogen atoms and halogen atoms generated from a plasma polymerization reaction. The charge transport layer according to the present invention is hereinafter referred to as a- The C film and charge generation layer are referred to as a-3i!15!).

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 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 fluorinated or fluorinated amorphous silicon germanium film. Although the charge transport layer does not have clear photoconductivity for visible light or light with a wavelength near semiconductor laser light, it has suitable transport properties, and also has good charging ability, durability, and weather resistance. Since the electrophotographic photoreceptor has excellent electrophotographic photoreceptor properties such as environmental pollution resistance and excellent light transmittance, it can provide an extremely high degree of freedom when forming a laminated structure as a function-separated photoreceptor. In addition, the charge generation layer has excellent photoconductivity for visible light or light at a wavelength near the semiconductor laser tip, and is extremely thin compared to conventional amorphous silicon photoreceptors. It is something that can be put to good use.

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

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

There are many types of hydrocarbons that can be used, but examples of saturated hydrocarbons include methane, ethane, propane, butane,
Pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane,
tocosan, tricosane, tetracosan, pentacosan,
Normal paraffins such as hexacosane, heptacosane, octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, etc., as well as isobutane, isopentane, neopentane, isohexane, neohexane, 2,3-dimethylbutane, 2-methylhexane, 3- Ethylpentane, 2,2-dimethylpentane, 2
．． 4-dimethylpentane, 3,3-dimethylpentane,
Tributane, 2-methylhebutane, 3-methylhebutane, 2,2-dimethylhexane, 2,2.5-dimethylhexane, 2,2.3-trimethylpentane, 2.2.4
Isoparaffins such as -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 -Olefins such as 2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-nonene, 1-decene, and allene, methylalene, butadiene, pentadiene, hexadiene,
Diolefins such as cyclopentadiene, triolefins such as ocimene, allocimene, myrcene, hexatriene, acetylene, butadiyne, etc.
゜3-pentadiyne, 2.4-hexadiyne, methylacetylene, 1-butyne, 2-butyne, 1-pentyne, 1
-Hexyne, 1-heptyne, 1-octyne, l-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, bodocarprene, mirene, and other terpenes, as well as steroids, are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, bunidocumene, mesitylene, prenitene, isodurene, durene,
Pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, piphenyl, terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

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

The amount of hydrogen atoms contained in a-CI51 in the present invention is inevitably determined from the manufacturing aspect of using glow discharge, but it is approximately 3% of the total amount of carbon atoms and hydrogen atoms.
The content can range from 0 to 60 at%. Here, the content of carbon atoms and hydrogen atoms in the film can be determined by using a conventional method of organic elemental analysis, for example, CNH analysis.

The amount of hydrogen atoms contained in the a-C film in the present invention is
It varies depending on the form of the film-forming equipment and the conditions during film-forming, but
For example, increasing the substrate temperature, decreasing the pressure, decreasing the dilution rate of the raw material hydrocarbon gas, increasing the applied power,
Measures such as lowering the frequency of the alternating electric field, increasing the strength of the DC electric field superimposed on the alternating electric field, or a combination thereof have the effect of lowering the amount of hydrogen contained.

The thickness of the a-C film as the charge transport layer in the present invention is S to 5 in order to be used in a normal electrophotographic process.
A suitable thickness is 0 μm, particularly 7 to 20 μm; if it is thinner than 5 μm, sufficient copy image density cannot be obtained because the charging potential is low. Moreover, if it is thicker than 50 μm, it is not preferable in terms of productivity.

This a-C film has high light transmittance, high dark resistance, and is rich in charge transport properties, and even if the film thickness is 5 μm or more as mentioned above, carriers are transported without being trapped and contribute to bright attenuation. is possible.

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

In the present invention, in addition to hydrocarbons, a nitrogen compound is used as a raw material for adding at least nitrogen atoms into the a-C film. The phase state of the nitrogen compound does not necessarily have to be a gas phase at room temperature and normal pressure; it can be used in either a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It is. Examples of nitrogen compounds include nitrogen, inorganic compounds such as ammonia,
Organic compounds having functional groups such as amino groups (-NH2) and cyano groups (-CN), and nitrogen-containing heterocycles 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, heptylamine, octylamine, nonylamine, decylamine, and undecyl. amine,
Dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyamylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, allylamine, diallylamine, Triallylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, toluidine, benzylamine, dibenzylamine, tribenzylamine, diphenylamine, triphenylamine, naphthylamine , ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diaminoheptane, 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 pyrrole,
Viroline, pyrrolidine, oxazole, thiazole, imidazole, imidacilline, imidazolidine, pyrazole, birapurine, pyrazolidine, triazole, tetrazole, pyridine, piperidine, oxazine, morpholine, thiazine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, indole, indoline, benzo oxazole, indazole, benzimidazole,
quinoline, cinnoline, phthalazine, phthalocyanine,
Quinazoline, quinxaline, carbazole, acridine, 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 transportability is not ensured, the film formation rate is slow, and furthermore, it is likely to deteriorate over time after film formation.

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

In the present invention, the amount of nitrogen atoms contained as a chemical modifier can be controlled mainly by increasing or decreasing the amount of the nitrogen compound introduced into the reaction chamber in which the plasma reaction is performed. If the amount of nitrogen compounds introduced is increased,
It is possible to increase the amount of nitrogen atoms added into the a-C film according to the present invention, and conversely, by decreasing the amount of nitrogen compounds introduced, it is possible to increase the amount of nitrogen atoms added into the a-C film according to the present invention. It is possible to reduce the amount added.

In the present invention, in addition to hydrocarbons, halogen compounds are used to add at least halogen atoms into the a-C film. Here, the halogen atom refers to a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The phase state of the halogen compound does not necessarily have to be a gas phase at room temperature and normal pressure; it can be used in either a liquid phase or the same phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. be. Examples of halogen compounds include fluorine, chlorine, bromine, iodine, hydrogen fluoride, chlorine fluoride, bromine fluoride,
Iodine fluoride, hydrogen chloride, bromine chloride, iodine chloride, hydrogen bromide,
Inorganic compounds such as iodine bromide and hydrogen iodide, and organic compounds such as alkyl halides, aryl halides, styrene halides, polymethylene halides, and heroform are used. Examples of alkyl halides include methyl fluoride, methyl chloride, methyl bromide, methyl iodide, ethyl fluoride, ethyl chloride, ethyl bromide, ethyl iodide, propyl fluoride, propyl chloride, propyl bromide, and Propyl chloride, butyl fluoride, butyl chloride, butyl bromide, butyl iodide, amyl fluoride, amyl chloride, amyl bromide, amyl iodide, hexyl fluoride, hexyl chloride, hexyl bromide, hexyl iodide, fluoride Heptyl chloride, hebutyl chloride, hebutyl bromide, hebutyl iodide, octyl iodide, 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. Examples of halogenated styrene include chlorstyrene,
Bromstyrene, iodostyrene, fluorostyrene,
etc. are used. Examples of halogenated polymethylene include methylene chloride, methylene bromide, methylene iodide,
Ethylene chloride, ethylene bromide, ethylene iodide, trimethylene chloride, trimethylene bromide, trimethylene iodide,
Butane dichloride, butane dibromide, butane dichloride, pentane dichloride, pentane dibromide, pentane dichloride, hexane dichloride, hexane dibromide, hexane dichloride, hebutane dichloride, hebutane dibromide, Used are hebutane dichloride, octane dichloride, octane dibromide, octane dichloride, nonane dichloride, nonane dibromide, decane dichloride, decane diiodide, and the like. Examples of heloform include fluoroform, chloroform, bromoform, iodoform, and the like.

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

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

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

In the present invention, silane gas, disilane gas, or fluorinated silane gas is used to form the a-Si film. Furthermore, germane gas is used to contain germanium atoms.

The content of germanium atoms contained in the a-3i 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-Si film in the present invention is important.

The amount of hydrogen atoms or fluorine atoms contained in a-3ill in the present invention is necessarily determined from the manufacturing aspect of using glow discharge, but it is determined based on the total amount of silicon atoms and hydrogen atoms or silicon atoms and fluorine atoms. Approximately 10 to 35
Contains atomic%. Here, the content of hydrogen atoms or fluorine atoms in the film can be determined by using conventional methods of elemental analysis, such as ONH analysis and Auger analysis.

The film thickness of a-SiJIg as a charge generation layer in the present invention is 0.0000.
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 furthermore, in the laminated structure with the a-C film, which is the most distinctive feature of the present invention, it is highly efficient < a-CI! ! It is possible to inject generated carriers into the layer 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.

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 positively charged, for example, by a corona charger, and then exposed to image light, the holes generated in the charge generation layer (3) are transferred to the charge transport layer (2) in Figure 1.
Electrons generated by charge generation 7EJ (3) travel through the charge transport layer (2) toward the surface of the photoreceptor, and in FIG. Charge generation layer (3
) The holes generated at Ff(2
) through the conductive substrate (1), and at the same time electrons generated in the charge generation layer (3) travel through the charge transport layer (2) on the surface side toward the surface of the photoreceptor. The formation of an electrostatic latent image with guaranteed brightness decay takes place. 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, as a further embodiment, a charge transport N (2), a charge generation layer (3) and a surface protective layer (
4) is shown in a structure formed by sequentially stacking them. In other words, it corresponds to the form shown in Fig. 1 with a surface protective layer provided, but
In the form of FIG. 1, since the outermost surface is an a-Si film with poor moisture resistance, in many cases it is preferable to provide a surface protective layer in order to ensure practical humidity stability. Second
In the case of the configurations shown in Figures and Figure 3, the outermost surface is a with excellent durability.
- Since it is a C film, there is no need to provide a surface protective layer, but for the purpose of adjusting the consistency with various elements in the copying machine, such as preventing stains on the surface of the photoreceptor due to adhesion of developer, surface protection Providing layers can also be an alternative form.

FIG. 5 shows, as a further embodiment, an intermediate N (5), a charge generation Fj (3) and a charge transport layer (
2) is shown in a structure formed by sequentially laminating layers. In other words, it corresponds to the form in which an intermediate layer is provided in the form shown in FIG.
In the illustrated embodiment, since the bonding surface with the conductive substrate is the a-3i film, in many cases it is preferable to provide an intermediate layer to ensure adhesiveness and injection blocking effect. Figures 1 and 3
In the case of the configuration shown in the figure, 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, there is no need to provide an intermediate layer. For the purpose of adjusting compatibility with the manufacturing process before the formation of the photosensitive layer, such as a pretreatment method, it is possible to provide an intermediate layer as a further form.

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. An a-C film according to the invention may also be used. However, if the material used is, for example, an insulating material as described in the conventional example, the film thickness must be kept at 5 μm or less to prevent generation of residual potential.

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

FIG. 7 shows a photoconductor manufacturing apparatus according to the present invention, and in the figure (701) to (706) are first to sixth tanks in which the raw material compound and carrier gas, which are in a gas phase at room temperature, are sealed, respectively. The tanks are the first to sixth control valves (707)
〜(712) and the first to sixth flow rate controllers (713)〜(
718). (719) to (721) in the figure
) are first to third containers filled with raw material compounds that are in a liquid or solid state at room temperature, and each container is heated by the first to third temperature controllers (722) to (724) for vaporization. In addition, each container has seventh to ninth control valves (725) to (727) and seventh to ninth flow rate controllers (725) to (727).
28) to (730). These gases are mixed in a mixer (731) and then sent into a reaction chamber (733) via a main pipe (732). The pipes along the way are
Heat can be applied to the gas obtained by vaporizing the raw material compound, which is in a liquid or solid phase at room temperature, by an appropriately placed pipe heater (734) so as not to condense on the way. Inside the reaction chamber, there is a ground electrode (735) and a power application electrode (
736) are installed facing each other, and each electrode can be heated by an electrode heater (737). Power application type I
I (736) is connected to a frequency power source (739) and a low frequency power matching device (738) via a matching device for low frequency power (738).
A low frequency quantity 1 (741) is connected to the i-current power supply (743) through a low-pass filter (742), and power with different frequencies can be applied by a connection selection switch (744). There is. Reaction chamber (733)
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 by an exhaust system selection valve (746).
) through a diffusion pump (747L oil rotary pump (74
8), or cooling exclusion device (749), mechanical booster pump (750), oil rotary pump (748)
This is done by For exhaust gas, an even more suitable exclusion bag! After being rendered safe and harmless by m (753), it is exhausted into the atmosphere. These exhaust system piping can also be heated by appropriately placed piping heaters (734) to prevent the vaporized gas from the raw metal material, which is in a liquid or solid phase state at room temperature, from condensing on the way. has been done. For the same reason, the reaction chamber (733) can also be heated by a reaction chamber heater (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 type w1 (735), but it may also be fixed to the power application electrode (736), or roughly arranged 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 is 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 an electrode heater (837) is arranged outside. The conductive substrate (852) is rotatable using an external drive motor (854).

The reaction chamber used for photoreceptor production is preliminarily heated by a diffusion pump.
The pressure is reduced to about 0-4 to 10-6 Torr, and the degree of vacuum is confirmed and the gas adsorbed inside the device is desorbed. At the same time, an electrode heater heats the electrode and the conductive substrate fixedly disposed on the electrode to a predetermined temperature. If necessary, an undercoat layer or a charge generation layer may be provided in advance on the conductive substrate in order to obtain a desired photoreceptor structure from among those described above. The present apparatus or a separate apparatus may be used to provide the undercode 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 state. After the gas flow rate is stabilized, a connection selection switch is used to select, for example, a high frequency power source, and high frequency power is applied to the power application electrode.

A discharge is started between the two electrodes, and over time a film of the same phase is formed on the substrate. The a-3i film or the a-C film can be formed arbitrarily by changing the raw material gas. Films with different compositions can be laminated by once stopping the discharge, changing the source gas composition, and then restarting the discharge. It is also possible to gradually change only the raw material gas flow rate while sustaining the discharge, and to stack films of different compositions with a gradient.

The film thickness is controlled by the reaction time, and when a predetermined film thickness and laminated structure are reached, the discharge is stopped to obtain a photoreceptor according to the present invention. Next, the first to ninth control valves are closed to sufficiently exhaust the inside of the reaction chamber. If the desired photoreceptor configuration is obtained, the vacuum in the reaction chamber is broken and the photoreceptor according to the present invention is taken out from the reaction chamber. Furthermore, in a desired photoreceptor configuration,
If a charge generation layer or an overcoat layer is required, the photoreceptor according to the present invention can be fabricated by using the present device as is, or by breaking the vacuum and transferring it to another device to provide these layers. get.

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

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

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Control valve (707
, 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 nitrogen gas from the fourth tank (704). The first, second, third, and fourth flow rate controllers (713, 714, 715, and 716) each supply carbon tetrafluoride gas under an output pressure of 1.0 Kg/cm2.
It flowed inside. Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 190 seconds, the acetylene gas flow rate to 45 seconds, the nitrogen gas flow rate to 7 seconds, and the carbon tetrafluoride gas flow rate to 10105e. Through the mixer (731), 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), use an aluminum substrate measuring 50 mm long x 50 mm wide x 3 mm thick, heat it to 200°C in advance, and when the gas flow rate and pressure are stable, set the connection selection switch ( 744), and applied 200 Watts of power to the power application electrode (736) at a frequency of 13.56 MHz to perform a plasma polymerization reaction for about 2 hours and 40 minutes.
A 15 μm thick a-C film 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 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 0.8 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 37A section valve (709), and the sixth control valve (712) are released, and the first tank (701) is opened.
hydrogen gas from the tank, tetrafluorosilane gas from the second tank (702), germane gas from the third tank (703), and silane gas from the sixth tank (706) at an output pressure of IKg/
The first, second, third, and sixth flow controllers (under cm2)
713, 714, 715, and 718). Adjust the scale of each flow rate side t1] to set the flow rate of hydrogen gas to 200 sec and the flow rate of silane tetrafluoride gas to 50 sec.
m, the flow rate of germane gas was set to 6 sCCm1, and the flow rate of silane gas was set to 50 sec, and the flow rate was allowed to flow into the reaction chamber (733). After each flow rate stabilized, the reaction chamber (73
3) The pressure regulating valve (745) was adjusted so that the pressure inside was 0.9 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 230°C.
With the gas flow rate and pressure stable, turn on the high frequency power supply (73
9), the power application electrode (
736) to generate a glow discharge. This discharge was performed for 5 minutes, and the thickness was 0.3 μm.
A charge generation layer was obtained.

The obtained a-Sillff was subjected to ONH analysis in metal (
EMGA-1300 manufactured by Itaba Seisakusho) and Auger analysis revealed that the contained hydrogen atoms were 18 at%, fluorine atoms were 5 at%, and germanium atoms were 11 at%, based on the total constituent atoms.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, 3 when positively charged! II constant values are shown in parentheses, the highest charging potential is -580V (+720V),
That is, since the total photoreceptor film thickness is 15°3um, 1μ
The charging ability per meter was extremely high at 38 .mu.m (48 V/.mu.m), and from this it was understood that the material had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 19 seconds (approximately 24 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential, and the amount of light required was 3.2 lux · seconds (4.3 lux · seconds), and from this we can understand that it has sufficient photosensitivity performance.

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

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

＾After pouring, as shown in Fig. 1, using the manufacturing apparatus according to the present invention,
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided 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 applied to the first, second, third, and
and fourth flow rate controller (713, 714, 715, and 7
16) It was allowed to flow into the interior. Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 60 seconds, the ethylene gas flow rate to 60 seconds, I! The flow rate of nitrogen oxide gas is 16
The flow rate of SCCm and carbon tetrachloride gas is set to 20 sec, and the mixture is passed through an intermediate mixer (731).
It flowed into the reaction chamber (733) from the main pipe (732). After each flow rate became stable, the pressure regulating valves (74, 5) were adjusted so that the pressure in the reaction chamber (733) was 2°0 Torr. On the other hand, as a conductive substrate (752), 1f
Using an aluminum substrate of 50 x width 50 x thickness 3 mm,
After heating the gas to 240°C in advance and stabilizing the gas flow rate and pressure, turn on the high frequency power source (739) that was previously connected using the connection selection switch (744), and apply 200 Watt to the power application electrode (736). Power at frequency 13.
A plasma polymerization reaction was performed for about 3 hours and 15 minutes by applying a frequency of 56 MHz, and a 15 μm thick film 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.

When the a-C film obtained as described above was subjected to organic elemental analysis, 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 halogen atoms, ie, 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 221st node valve (708) and the 6th control valve (712) are released, hydrogen gas is supplied from the first tank (701), Germanic gas is supplied from the second tank (702), and the sixth tank (70
6) was flowed into the first, second, and sixth flow controllers (713, 714, and 718) under an output pressure of IKg/cm2. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec, the germane gas flow rate to 0.6 secms, and the silane gas flow rate to 1010 sec.
05e to flow into the reaction chamber (733). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 0.8 Torr. On the other hand, the conductive substrate (752) on which the a-C film has been completely formed is heated to 250°C, and with the gas flow rate and pressure stable, it is heated at a frequency of 13.56 MHz from a high frequency power source (739). 3 to the power application electrode (736)
A power of 5 Watts was applied to generate glow discharge.

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

ONH analysis in metal (EMGA-1300 manufactured by Itaba Manufacturing Co., Ltd.) and Auger analysis were performed on the obtained a-Si crotch, and it was found that the hydrogen atoms that could be contained were 2 for all constituent atoms.
The content of germanium atoms was 0 at%, and the content of germanium atoms was 1 at%.

Characteristics: When the obtained photoreceptor was used 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 -520V (+640V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 34 .mu./.mu.m (42 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 13 seconds (approximately 16 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, white light was used to attenuate the surface potential to 20% of the highest charging potential, and the amount of light required was 1.3 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 amount of light required was 8.
3erg/cm2 (12,2erg/am2),
From this, it was understood that the material 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.

Implementation 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,
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. into the vessels (713, 715, and 716).

At the same time, styrene gas is supplied from the first container (719) to the first temperature control W (722) at the seventh flow rate controller (722) at a temperature of 35°C.
728). Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 60 seconds, the styrene gas flow rate to 30 seconds, and the nitrogen gas flow rate to 8 seconds.
, and the flow rate of carbon tetrafluoride gas is set to 30 seconds, and the main pipe (7
32) into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) reaches 2°0T.
The pressure control valve (745) was adjusted so that the

On the other hand, as the conductive substrate (752), ASOX horizontal 50
× Using an aluminum substrate with a thickness of 3 mm, heat the temperature at 180°C in advance.
After heating to , and with the gas flow and pressure stable,
Turn on the low frequency power supply (741) that has been connected in advance using the connection selection switch (744), and connect the power application electrode (736).
) was applied with a power of 200 Watts at a frequency of 170 KHz to carry out a plasma polymerization reaction for about 50 minutes to form a 15 μm thick a-C film as a charge transport layer on the conductive substrate (752). After completing the film formation, stop applying power and
The control valve was closed and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 47 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, that is, fluorine atoms, is 6.1 at%, approximately 1.0 at%, based on the total constituent atoms. The amount of nitrogen atoms was 2.1 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),
2nd QOJ control valve (708) and 6th control valve (712)
hydrogen gas from the first tank (701), germane gas from the second tank (702), and hydrogen gas from the sixth tank (702).
06) was flowed into the first, second, and sixth flow controllers (713, 714, and 718) under an output pressure of IKg/am2. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec, the germane gas flow rate to 2 sccm, and the silane gas flow rate to 10100.
5e and flowed into the reaction chamber (733). After each flow rate stabilizes, the pressure in the reaction chamber (733) becomes 0.
．． The pressure regulating valve (745) was adjusted to 8 Torr. On the other hand, the conductive substrate (752) on which a-CylJ is formed is heated to 250°C, and with the gas flow rate and pressure stabilized, it is powered by a high frequency power source (739) at a frequency of 13.56 MHz. Power application electrode (736)
A power of 35 Watts was applied to generate a glow discharge.

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

When the obtained a-3i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Manufacturing Co., Ltd.) and Auger analysis, it was found that the hydrogen atoms contained were 2% of the total constituent atoms.
The content of germanium atoms was 0 at%, and the content of germanium atoms was 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 during positive charging are shown in parentheses, and the highest charging potential is -510V (+610V).In other words, since the total photoreceptor film thickness is 15°3μm, the charging capacity per μm is 33V. /μm (40V/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 surface potential in the dark is approximately 1; Ml+ (approximately 15 seconds), which indicates that it has sufficient charge retention performance. It was done. In addition, after initial charging to the highest charging potential, the brightness was attenuated using white light to a surface potential of 20% of the highest charging potential, and the required amount of light was 1.2 lux · seconds (1.6 lux · seconds), and from this it was understood that it had sufficient photosensitivity performance. Also, after initial charging to the highest charging potential, what was the amount of light required to attenuate the surface potential to 20% of the highest charging potential using semiconductor laser light (wavelength: 780 nm)? ,
6 erg/cm2 (9.5 erg/am2), 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. 4 control valve (707
, 708, 709, and 710), hydrogen gas from the first tank (701), butadiene gas from the second tank (702), nitrogen 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/cm2.
It flowed inside. Then, adjust the scales of each flow rate controller to set the flow rate of hydrogen gas to 180 seconds, the flow rate of butadiene gas to 40 seconds, the flow rate of nitrogen gas to 7 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 stabilized, the pressure inside the reaction chamber (733) reached 2.0 Torr.
The pressure regulating valve (745) was adjusted so that the temperature was r. On the other hand, as the conductive substrate (752), use an aluminum substrate measuring 50 mm long x 50 mm wide x 3 mm thick, heat it to 180 degrees Celsius in advance, and with the gas flow rate and pressure stable, connect the connection selection switch ( The low frequency power source (741) connected to the conductive substrate (744) is turned on, and 200 Watt power is applied to the power application electrode (736) at a frequency of 500 KHz to perform a plasma polymerization reaction for about 30 minutes. 752), a 15 μm thick a-C film was formed thereon as a charge transport layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 40 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, fluorine atoms, was 4.1 atomic % based on the total constituent atoms, and the amount of nitrogen atoms was roughly 0.7 atomic % based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks were replaced, and the first control valve (7O7)
2nd FJEJ control valve (708) and 6th control valve (712)
) from the first tank (701) and hydrogen gas from the second tank (701).
Germanic gas from the tank (702) and the sixth tank (
706), the silane gas is controlled at the 11th, 2nd, and 6th flow rate under the output pressure IKg/am2! (713,714,
and 718). Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec, the germane gas flow rate to 20 sec, and the silane gas flow rate to 101 sec.
005e and flowed into the reaction chamber (733).

After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 1.0 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 250°C, and with the gas flow rate and pressure stable, it is heated at a frequency of 13°56MHz from a high frequency power source (739). 4 to the power application electrode (736)
A glow discharge was generated by applying a power of 5 Watts.

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

When the resulting a-Si film was subjected to ○NH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho) and Auger analysis, the number of hydrogen atoms that could be contained was 2 for all constituent atoms.
The content of germanium atoms was 0 atom %, and the content of germanium atoms was 30 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 -380V (+430V), that is,
Since the total photoreceptor film thickness was 15.3 μm, the charging ability per 1 μm was extremely high at 25 μm/μm (28 V/μm), 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 10 seconds (approximately 11 seconds).
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 required amount of light was 3.4 lux·sec (3.9 lux·sec). seconds), and from this it was concluded that the film 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), 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 eleventh second, third, and fourth flow controllers (713, 714, 715, and 716) under an output pressure of 1.0 Kg/cm2, respectively. Then, by adjusting the scales of each flow rate controller, the flow rate of hydrogen gas was 1203 CCm, the flow rate of butadiene gas was 603 CCm%, the flow rate of ammonia gas was 6 s c c mz, and the flow rate of carbon tetrafluoride gas was 1.
Set it so that it is 60 sec, and mixer (73
1) and flowed into the reaction chamber (733) from the main pipe (732).

After each flow rate stabilizes, the pressure inside the reaction chamber (733) decreases to 2. The pressure control valve (745) was adjusted so that it became ITorr. On the other hand, as a conductive substrate (752),
Using an aluminum substrate measuring 0 x width 50 x thickness 3 mm, it was preheated to 120°C, and with the gas flow rate and pressure stabilized, a low frequency power source ( 741) and apply 140W of power to the power application electrode (736) at a frequency of 400K.
Plasma polymerization reaction was carried out for about 1 hour and 20 minutes by applying the voltage under Hz, and a 15 μm thick a-
A C film was formed as a charge transport layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms that could be contained was 51 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, fluorine atoms, is 17.0 at % based on the total constituent atoms, and the amount of nitrogen atoms is 2.4 at % based on the total constituent atoms.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
The second control valve (708) and the sixth control valve (712) are released, hydrogen gas is supplied from the first tank (701), Germanic gas is supplied from the second tank (702), and the sixth tank (706
) under an output pressure of IKg/cm2.
, second, and sixth flow rate controllers (713, 714, and 7
18) It was allowed to flow into the interior. Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 200 sec, the flow rate of germane gas to 6 sec, and the flow rate of silane gas to 11005 cc.
was set to flow into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 0.9
The pressure control valve (745) was adjusted so that the pressure was Torr. On the other hand, a conductive substrate (75
2) is heated to 250°C, and with the gas flow rate and pressure stable, a frequency of 13 is applied from the high frequency power supply (739).
．． 40W to power application electrode (736) under 56MHz
A glow discharge was generated by applying a power of tt.

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

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

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -230V (+280V), 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 15 V/.mu.m (18 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

Also, the time required for dark decay from Vmax to 90% of Vmax in the dark is approximately 4 seconds (approximately 5 seconds).
From this, it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated using white light to a surface potential of 20% of the highest charging potential, and the amount of light required was 3.3 lux.
seconds (3°1 lux·sec), 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.

[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 1, 1988

Claims (1)

[Claims] In a functionally separated photoreceptor having a charge generation layer and a charge transport layer, the charge transport layer is a hydrogenated amorphous carbon film containing at least nitrogen atoms and halogen atoms; 1. A photoreceptor comprising a fluorinated or fluorinated amorphous silicon germanium film.