JPS6382463A - 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. oxygen and halogen and an electric charge generating layer contg. specific atoms. CONSTITUTION: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 oxygen and halogen. The layer 3 consists of the hydrogenated or fluorinated amorphous silicon germanium film contg. phosphorus or/and fluorine. 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 The present invention relates to a photoreceptor having a charge generation layer and a charge transport layer.

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

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

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

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

It is possible.

By the way, the amorphous carbon film itself is known as a plasma organic polymer 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 5science), Volume 17, pages 885 to 892, the same author also reported in the 1979 American Chemical Society that all organic compounds can be prepared 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 <1018 Ωcm, like ordinary polyethylene films. Or at least it was used with the recognition that it was such a membrane. Due to the same recognition, its actual use in electrophotographic photoreceptors has been limited to protective layers, adhesive layers, blocking layers, or insulating layers, and has only been used as so-called undercoat layers or overcoat layers.

For example, JP-A-59-28161 discloses a photoreceptor in which a plasma-polymerized polymer layer having a network structure is provided on a substrate as a blocking layer and an adhesive layer, and an amorphous silicon layer is provided thereon. ing. Japanese Patent Application Publication No. 5
Publication No. 9-38753 discloses that a plasma polymerized film with a high resistance of 1013 to 1015 Ωcm, which is generated from a mixed gas of oxygen, nitrogen, and hydrocarbon, is provided on a substrate as a blocking layer and an adhesive layer by 10 to 100 people. A photoreceptor is disclosed that includes an amorphous silicon layer. Unexamined Japanese Patent Publication 1987-
'136742 discloses a photosensitive material 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. The body is 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 μm or less in terms of residual charge.

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

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

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

All of these disclosures are inventions in which a so-called overcoat layer is provided on the surface of a photoreceptor, and there is no disclosure of charge transport properties, and they do not solve the above-mentioned essential problems of a-5i. .

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

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

Philosophical Magazine published in 1976 by
Magazine) Volume 33, pages 935 to 94
Since it was reported on page 9 that it is a material whose polarity can be controlled, attempts have been made to apply it to various photoelectric devices. Regarding the application to photoreceptors, for example,
No. 62254, Japanese Patent Application Laid-open No. 119356/1983,
JP-A-57-177147, JP-A-57-119
357, JP 57-177149, JP 57-119357, JP 57-17714
Publication No. 6, JP-A-57-177148, JP-A-5
Amorphous silicon photoreceptors containing carbon atoms are disclosed in JP-A No. 7-174448, JP-A-57-174449, JP-A-57-174450, etc., but all of them are amorphous silicon photoconductors. The purpose is to adjust the properties using carbon atoms, and
Amorphous silicon itself requires a thick film.

As mentioned above, conventionally, plasma organic polymer films used in electrophotographic photoreceptors have been used as so-called undercoat layers or overcoat layers; It is a film that does not require any function, 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. Therefore, when laminated with a hydrogenated or fluorinated amorphous silicon germanium film containing at least one of phosphorus atoms and boron atoms, it has charge transport properties and easily begins to exhibit suitable electrophotographic properties. I found out. Although the theoretical interpretation has many unclear points even for the present inventors, it is not possible to discuss it in detail. A hydrogenated or fluorinated amorphous silicon germanium film in which a band structure formed by electrons in a stable energy state, such as π electrons, unpaired electrons, residual free radicals, etc., contains at least one of phosphorus atoms and boron atoms. Because it has a similar energy level in the conduction band or valence band to the band structure formed by Carriers are easily injected into the hydrogenated amorphous carbon film containing oxygen atoms and halogen atoms, and roughly speaking, these carriers are combined with oxygen atoms and halogen atoms due to the action of the electrons in the relatively unstable energy state mentioned above. It is presumed that this is because the hydrogenated amorphous carbon film can run suitably through the hydrogenated amorphous carbon film containing the above.

By utilizing this new knowledge, the present invention solves all the above-mentioned essential problems of amorphous silicon photoreceptors, and also uses organic plasma polymerized films, especially oxygen A thin film of hydrogenated or fluorinated amorphous silicon germanium using a hydrogenated amorphous carbon film containing atoms and halogen atoms as a charge transport layer, and containing at least one of phosphorus atoms and boron atoms. It is an object of the present invention to provide a photoreceptor using as a charge generation layer.

For adjusting the hinge.

That is, the present invention provides a functionally separated photoreceptor having a charge generation layer and a charge transport layer, in which the charge transport layer is made of hydrogenated amorphous carbon containing at least oxygen atoms and halogen atoms generated through a plasma polymerization reaction. The present invention relates to a photoconductor characterized in that the charge generation layer is a hydrogenated or fluorinated amorphous silicon germanium film containing at least one of phosphorus atoms and boron atoms (hereinafter referred to as the present invention). charge transport layer by a-C
The film and charge generation layer are referred to as a-3i film).

The present invention was developed because, in conventional amorphous silicon photoreceptors, amorphous silicon, which has an excellent function as a charge generation layer, is also used as a charge transport layer, which requires only charge transport ability even if it does not have charge generation ability. This was done to solve these problems.

That is, the present invention provides a hydrogenated amorphous carbon film containing at least oxygen atoms and halogen atoms 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. Although the charge transport layer does not have clear photoconductivity for visible light or light with a wavelength near semiconductor laser light, it has suitable transport properties, and has good charging ability, durability, and weather resistance. It has excellent electrophotographic photoreceptor performance such as durability and environmental pollution resistance, and is also excellent in light transmission, so it provides an extremely high degree of freedom when forming a laminated structure as a function-separated photoreceptor. .

In addition, the charge generation layer has excellent photoconductivity for visible light or light with a wavelength near semiconductor laser light, and has an extremely thin film thickness compared to conventional amorphous silicon photoreceptors. In the present invention, it is important to take advantage of
Organic compound gases, especially hydrocarbon gases, are 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, hexacosane, heptacosane, octacosane, 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-trimethylbentane, 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, 1-nonine, 1-decyne, etc. are used.

Examples of alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cycloundecane, and cyclotetrate.

Cycloparaffins such as can, cyclopentadecane, cyclohexadecane, cycloolefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, limonene, terpinolene, phelandrene, silvestrene, thuene, karene. , pinene, bornylene, camphuene, fenchen, cycloundecane, tricyclene, bisabolene, zingiberene,
Terpenes such as curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, campholene, phylloclatene, bodocarbrene, mirene, and steroids are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, pseudocumene, mesitylene, prenitene, isodurene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, biphenyl, terphenyl, diphenylmethane. , triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin,
Anthracene, phenanthrene, etc. are used.

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

The amount of hydrogen atoms contained in the a-C film of the present invention is inevitably determined from the manufacturing aspect of using glow discharge, but it is approximately 30 to 60 at% of the total amount of carbon atoms and hydrogen atoms. . Here, the content of carbon atoms and hydrogen atoms in the film is determined by a conventional method of organic elemental analysis, for example, CN
This can be determined by using H analysis.

The amount of hydrogen atoms contained in the a-C film in the present invention 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, lowering the pressure, lowering 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 5 to 5
A suitable thickness is 0 μm, especially 7 to 20 μm, and if it is thinner than 5 μm, sufficient copying 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.

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

In the present invention, in addition to hydrocarbons, oxygen compounds are used to add at least oxygen atoms into the a-C film. The phase state of the oxygen compound does not necessarily have to be a gas phase at room temperature and normal pressure; it can be used in either a liquid phase or the same phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. be. 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'It group (RCO
-, -CRO), a ketone group (>Co), an ether bond (-〇-), an ester bond (-Coo-), an oxygen-containing heterocycle, or an organic compound having a functional group or bond, etc. It will be done. 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 the organic compound having an aldehyde group include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, acrolein, benzaldehyde, and furfural. Examples of organic compounds having an acyl group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, valmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, toluic acid, and salicylic acid. , silica and acid, naphthoic acid, phthalic acid, furanic acid, etc. are used.

Examples of organic compounds having a ketone group include acetone, ethyl methyl ketone, methyl propyl ketone, butyl methyl ketone, binacolon, diethyl ketone, methyl vinyl ketone, mesityl oxide, methyl hebutenone,
Cyclobutanone, cyclopentanone, cyclohexanone, acetophenone, propiophenone, butyrophenone, parellophenone, dibenzylketone, acetonaphtone, 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, 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, propyl propionate, 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. used. Examples of heterocyclic compounds containing oxygen include furan, oxazole, furazane, pyran, oxazine, morpholine, benzofuran, banzoxazole, chromene, chroman, dibenzofuran, xanthine, phenoxazine, oxolane, dioxolane, oxathiolane, oxadiazine, benzisoxazole, etc. are used.

In the present invention, the amount of oxygen atoms contained as a chemical modifier is 7.0 atom % or less based on the total constituent atoms. Here, the content of oxygen atoms in the film is determined by the standard method of elemental analysis.
For example, we can learn this through 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, and carbon oxide gas, have a strong etching effect, and by increasing their flow rate, the amount of oxygen atoms added to the film can be increased. If this is attempted, the film formation rate decreases, which is inconvenient when forming a charge transport layer that requires a certain thickness. 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. By increasing the amount of oxygen compounds introduced, it is possible to increase the amount of oxygen atoms added to the a-C film according to the present invention, and conversely, by decreasing the amount of oxygen compounds introduced, the amount of oxygen atoms added to the a-C film according to the present invention can be increased. It is possible to reduce the amount of oxygen atoms added to the a-C film due to the a-C film.

In the present invention, in addition to hydrocarbons, halogen compounds are used to add at least halogen atoms to a-Clll. Here, halogen atoms include fluorine atoms,
Refers to chlorine atoms, bromine atoms, and iodine atoms. The phase state of the halogen compound does not necessarily have to be a gas phase at room temperature and pressure, but can be melted, evaporated, or evaporated by heating or reduced pressure.
As long as it can be vaporized through sublimation or the like, either liquid phase or solid phase can be used. Examples of halogen compounds include:
Inorganic compounds such as fluorine, chlorine, bromine, iodine, hydrogen fluoride, chlorine fluoride, bromine fluoride, iodine fluoride, hydrogen chloride, bromine chloride, iodine chloride, hydrogen bromide, iodine bromide, hydrogen iodide, etc. Organic compounds such as alkyl halide, aryl halide, styrene halide, polymethylene halide, 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, propyl iodide, butyl fluoride, butyl chloride, butyl bromide,
Butyl iodide, amyl fluoride, amyl chloride, amyl bromide, amyl iodide, hexyl fluoride, hexyl chloride, hexyl bromide, hexyl iodide, heptyl fluoride, hebutyl chloride, hebutyl bromide, heptyl 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. Examples of the halogenated aryl include fluorobenzene, chlorobenzene, bromobenzene, 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 diiodide, hebutane dichloride, hebutane dibromide, hebutane dichloride, octane dichloride, Octane dibromide, octane shoide, nonane dichloride, nonane dibromide, decane dichloride, decane diiodide, etc. are used. Examples of heroform include:
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 also no longer guaranteed. When the amount of halogen atoms is higher than 25 at %, the halogen atoms, which had guaranteed suitable charge transport properties and prevention of residual potential generation with the addition of am, will conversely cause a decrease in charging ability and, more particularly, after aging. It has the effect of lowering the dark resistance of the cell, leading to a decrease in charge retention ability during storage for several months. Furthermore, film-forming properties are not necessarily guaranteed, leading to peeling of the film, oily state, or powdery state. Therefore, the range of the amount of halogen atoms added in the present invention is important.

In the present invention, the amount of halogen atoms 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, 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-3i film. Furthermore, phosphine gas or diborane gas is used as a raw material gas for incorporating phosphorus atoms or boron atoms as chemical modifiers into the 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 the sensitivity increases over a wide range from the short wavelength region to the long wavelength region (
Although it is preferable because the exposure source can be selected, it is not preferable to add germanium atoms in an amount greater than 30 at % (because if it is contained, the charging ability will be lowered. Therefore, in the a-8i film in the present invention, The content of germanium atoms contained in is important.

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

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 can be 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-5i 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,
Furthermore, in the laminated structure with the a-C film, which is the most characteristic feature of the present invention, generated carriers can be efficiently injected into the a-C film, contributing to suitable bright attenuation.

The process of forming the a-5i film from the raw material gas in the present invention is carried out in the same manner as the case of forming the a-C film.

In the present invention, the amount of phosphorus atoms or Ellll atoms contained as a chemical modifier is mainly controlled by increasing or decreasing the amount of the aforementioned phosphine gas or diborane gas introduced into the reaction chamber in which the plasma reaction is performed. Is possible. By increasing the amount of phosphine gas or diborane gas introduced, it is possible to increase the amount of phosphorus atoms or boron atoms added to the a-Si film according to the present invention. By reducing the amount of phosphorus atoms or boron atoms introduced into the a-Si film according to the present invention, it is possible to reduce the amount of phosphorus atoms or boron atoms added to the a-Si film according to the present invention.

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 using a corona charger or the like and then used for image exposure, in FIG. 1, holes generated in the charge generation layer (3) pass through the charge transport layer (2). Electrons travel toward the conductive substrate (1), and in Figure 2, electrons generated by charge generation N (3) travel through the charge transport layer (2) toward the surface of the photoreceptor; Holes generated in the layer (3) travel toward the conductive substrate (1) through the charge transport layer (2) on the conductive substrate side, and at the same time travel through the charge generation layer (2) toward the conductive substrate (1).
The electrons generated in step 3) travel toward the surface of the photoreceptor through the charge transport layer (2) on the front side, forming an electrostatic latent image guaranteed to have suitable brightness attenuation. On the other hand, when the surface of the photoreceptor is negatively charged and then used for image exposure, the behavior of electrons and holes can be exchanged to understand the mobility of carriers. In FIGS. 2 and 3, the irradiation light for image exposure passes through the charge transport layer, but since the charge transport layer according to the present invention has excellent translucency, it forms a suitable latent image. Is possible.

FIG. 4 shows, as a further embodiment, a charge transport layer (2), a charge generation layer (3) and a surface protective layer (
4) is shown in a structure formed by sequentially stacking them. In other words, it corresponds to the form shown in Fig. 1 with a surface protective layer provided, but
In the form of FIG. 1, since the outermost surface is an a-3i film with poor moisture resistance, in many cases it is preferable to provide a surface protective layer in order to ensure practical humidity stability. Second
In the case of the configurations shown in Figures and Figure 3, the outermost surface is a with excellent durability.
- Since it is a C film, there is no need to provide a surface protective layer, but for the purpose of adjusting the consistency with various elements in the copying machine, such as preventing stains on the surface of the photoreceptor due to adhesion of developer, surface protection Providing layers can also be a further embodiment.

FIG. 5 shows, as a further embodiment, an intermediate layer (5), 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. That is, the second
This corresponds to the form shown in the figure with an intermediate layer provided, but in the form shown in Fig. 2, the bonding surface with the conductive substrate is an a-3i film, which ensures adhesiveness and injection blocking effect in most cases. It is preferable to provide an intermediate layer for this purpose. In the case of the configurations shown in FIGS. 1 and 3, since the bonding surface with the conductive substrate is the charge transport layer according to the present invention, which has excellent adhesiveness and injection blocking effect, it is not necessary to provide an intermediate layer. For the purpose of adjusting compatibility with the manufacturing process before forming the photosensitive layer, such as a pre-treatment method for a conductive substrate, an intermediate layer may be provided as a further form.

FIG. 6 shows, as a 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). After these gases are completely mixed in the mixer (731), they are sent into the reaction chamber (733) via the 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 phase or the same phase state at room temperature, by an appropriately arranged pipe heater (734) so as not to condense on the way. Inside the reaction chamber, there is a ground electrode (735) and a power application electrode (
736) are installed facing each other, and each electrode can be heated by an electrode heater (737). A high frequency power supply (739) and a low frequency power matching box (740) are connected to the power applying electrode (736) via a matching box for high frequency power (738).
), low frequency power supply (741), low pass filter (
A DC power source (743) is connected via a power source (742), and power with different frequencies can be applied by a connection selection switch (744). The pressure inside the reaction chamber (733) can be adjusted by a pressure control valve (745), and the pressure inside the reaction chamber (733) can be reduced through an exhaust system selection valve (746), a diffusion pump (747), and an oil rotary valve. Pump (748)
, or by a cooling exclusion device (749), a mechanical booster pump (750), or an oil rotary pump (748). The exhaust gas is made safe and harmless by a suitable exclusion device (753) and then exhausted into the atmosphere. Regarding these exhaust system piping, the gas that is the vaporized raw material compound that was in the liquid or solid phase at room temperature is
Distribute appropriately to avoid condensation on the way! pipe heater (
734), heat can be applied. Reaction chamber (73
3) can also be heated by the reaction chamber heater (751) for the same reason, and a conductive substrate (751) is placed on the electrode arranged inside.
52) can be installed. In FIG. 7, a conductive substrate (75
2) is fixed to the ground type If+ (735), but the amount of power applied f! (736) may be fixedly arranged, or may be arranged roughly on both sides.

FIG. 8 shows another embodiment of the photoconductor manufacturing apparatus according to the present invention, which is similar to the photoconductor manufacturing apparatus according to the present invention shown in FIG. 7 except for the internal configuration of the reaction chamber (833). can be,
The appended numbers can be understood by replacing the 700s with 800s. In FIG. 8, the reaction chamber (83
3) A cylindrical conductive substrate (852) that also serves as the ground electrode (735) in FIG. 7 is installed inside, and an electrode heater (837) is placed inside. Conductive substrate (
852) There is also a cylindrical power application electrode (
836) is arranged, and an electrode heater (837) is arranged on the outside. The conductive substrate (852) is rotatable using an external drive motor (854).

The reaction chamber used for photoreceptor production is preliminarily heated by a diffusion pump.
The pressure is reduced to about 0-4 to 10-6 Torr, and the degree of vacuum is confirmed and the gas adsorbed inside the device is desorbed. At the same time, an electrode heater heats the electrode and the conductive substrate fixedly disposed on the electrode to a predetermined temperature. If necessary, an undercoat layer or a charge generation layer may be provided in advance on the conductive substrate in order to obtain a desired photoreceptor structure from among those described above. The present apparatus or a separate apparatus may be used to provide the undercoat layer or the charge generation layer. Next, the raw material gases are introduced into the reaction chamber from the first to sixth tanks and the first to third containers while being kept at a constant flow using the first to ninth flow rate devices, and the inside of the reaction chamber is controlled by the pressure regulating valve. Maintain constant vacuum. After the gas flow rate is stabilized, a connection selection switch is used to select, for example, a high frequency power source, and high frequency power is applied to the power application electrode.

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

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

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

Implementation 1 Using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided on the head.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. 3, and the fourth control valve (
707, 708, 709, and 710), and
Hydrogen gas from tank (701), second tank (702)
Acetylene gas, oxygen gas from the third tank (703), and carbon tetrafluoride gas from the fourth tank (704) were supplied to the first, second, third, and third tanks under an output pressure of 1.0 Kg/cm2, respectively.
and fourth flow rate controller (713, 714, 715, and 7
16) It flowed inside. Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 180 seconds, the acetylene gas flow rate to 40 seconds, and the oxygen gas flow rate to 4 seconds.
The flow rate of m1 and carbon tetrafluoride gas is set to 10105e, and the main pipe (
732) into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 2.0.
The pressure control valve (745) was adjusted so that the pressure was Torr. On the other hand, as the conductive substrate (752), an aluminum substrate of 5'OX x 50mm x 43mm was used in advance.
After heating to 50°C, and with the gas flow rate and pressure stable, turn on the high frequency power supply (739) that was previously connected using the connection selection switch (744), and connect the power application electrode (736). 200Watt power at frequency 13.56
A plasma polymerization reaction was carried out for about 3 hours by applying a voltage under MHz, and a 15 μm thick a-C was deposited on the conductive substrate (752).
The membrane 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) 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. At the same time, the fourth control valve (710)
110 with hydrogen gas from the fourth tank (704).
Diborane gas diluted to 0pp is output at an output pressure of 1°5Kg.
/cm2 into the fourth flow controller (716). Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 200 sec, the flow rate of germane gas to 6 sccm, the flow rate of silane gas to 11003 cc, and the flow rate of hydrogen gas to 1100 cc.
The flow rate of diborane gas diluted to pp. 10105e was set to 10105e, and the diborane gas was allowed to flow into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 1.0T.
The pressure control valve (745) was adjusted so that the

On the other hand, a conductive substrate (752) on which an a-C film is formed
is heated to 240°C, and when the gas flow rate and pressure are stable, the frequency is 13.5 from the high frequency power supply (739).
40W to power applied type TM (736) under 6MHz
A power of t was applied to generate a glow discharge. This discharge was performed 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 18 atomic % and the boron atoms were 10 atomic ppm based on the total constituent atoms.
, germanium atoms were 9.7 at%.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -590V (+580V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 39 V/.mu.m (38 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 19 seconds (approximately 20 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential.The amount of light required was 3.1 lux·sec (2.9 lux・Seconds), and from this, it was reasonable to have 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.

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. Control valve (707
, 708, 709, and 710), hydrogen gas from the first tank (701), ethylene gas from the second tank (702), oxygen gas from the third tank (703), and hydrogen gas from the fourth tank (704). Each output pressure of carbon chloride gas is 1
It was allowed to flow into the first, second, third, and fourth flow controllers (713, 714, 715, and 716) under 0 Kg/cm2. Then, adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 60 seconds and the ethylene gas flow rate to 60 seconds.
Set the flow rate of oxygen gas to 4 seconds and the flow rate of carbon tetrachloride gas to 20 seconds,
It flowed into the reaction chamber (733) from the main pipe (732) via an intermediate mixer (731). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 2.0 Torr.

On the other hand, the conductive substrate (752) takes -1,! Using an aluminum substrate of 50 x width 50 x thickness 3 mm,
After heating the gas to 0°C 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 connect the power application electrode (7
36) 200 W all power at frequency 13.56
A plasma polymerization reaction with a thickness of 15 μm was performed on the conductive substrate (752) by applying a plasma at about 3 MHz.
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.

When organic elemental analysis was performed on the a-C film obtained as above, the amount of hydrogen atoms contained was 42 at% based on the total amount of carbon atoms and hydrogen atoms, and according to Auger analysis, the amount of hydrogen atoms contained was The amount of halogen atoms, ie, chlorine atoms, was 469 atomic % based on the total constituent atoms, and the amount of oxygen atoms was roughly 1.0 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) 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.
, and the 6th flow rate system (utilities (713 and 718). At the same time, the 4th UfJ control valve (710) was released, and the boss fin diluted to 1100pp with hydrogen gas from the 4th tank (704) Gas output pressure 1.5Kg/cm
2 into the fourth flow controller (716).

Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200.
secm, germane gas flow rate is 6secm, silane gas flow rate is 101005e.

The flow rate of phosphine gas diluted to 1100 pp with hydrogen gas was set to 10105e, and the gas was allowed to flow into the reaction chamber (733). After each flow rate stabilizes, the reaction chamber (733
) so that the pressure in the pressure control valve ( ) becomes 0.8 Torr
745) was adjusted.

On the other hand, a conductive substrate (752) on which an a-C film is formed
is heated to 250°C, and when the gas flow rate and pressure are stable, the frequency is 13.5 from the high frequency power supply (739).
40Watt to the power application electrode (736) under 6MHz
electric power was applied to generate a glow discharge. This discharge was performed 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 20 at % of the total constituent atoms, and the phosphorus atoms were 11 atoms pm.
The content of s-germanium atoms was 10 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 -390V (+610V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 26 V/.mu.m (40 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 10 seconds (approximately 15 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. 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.

On the implementation side, 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. 707,70
9, and 710), hydrogen gas is supplied from the first tank (701), oxygen gas is supplied from the third tank (703), and the fourth tank (T.

4) Each output pressure of carbon tetrafluoride gas is 1.0 Kg/cm.
2, the first, third, and fourth flow controllers (713, 7
15, and 716).

At the same time, the styrene gas is transferred from the first container (719) to the first temperature controller (722) at a temperature of 35°C at a seventh flow rate IIJln.
The liquid flowed into the vessel (728). Then, the scales of each flow rate controller were adjusted to set the hydrogen gas flow rate to 60 seconds and the styrene gas flow rate to 30 seconds.

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
), use an aluminum substrate measuring 50 x 50 x 3 mm in thickness, 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 the film formation is completed, stop applying power, close the control valve, and close the reaction chamber (7
33) Thoroughly evacuated the inside.

When organic elemental analysis was performed on the a-C film obtained as described above, 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, contained was 6.1 at% based on the total constituent atoms, and the amount of oxygen atoms was 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),
The second control valve (708), the third control valve (709), and the sixth control valve (712) are released, hydrogen gas is released from the first tank (701), tetrafluorosilane gas is removed from the second tank (702), Germanic gas from the third tank (702) and the sixth
Silane gas is supplied from the tank (706) at an output pressure of IKg/c.
m2 into the eleventh second, third, and sixth flow rate limiters (713, 714, 715, and 718). At the same time, the fourth control valve (710) is opened, and diborane gas diluted to 1100 pp with hydrogen gas is supplied from the fourth tank (704) to the fourth tank under an output pressure of 1°5 Kg/cm2.
It was made to flow into the flow rate controller (716). Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 200 secms, the flow rate of silane tetrafluoride gas to 50 sec1, the flow rate of germane gas to 6 scCms, and the flow rate of silane gas to 50 sec.

The flow rate of diborane gas diluted to 1100pp with hydrogen gas was set to 1105cc, and the reaction chamber (7
33) There was an inflow into the interior. After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 0°9 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 230°C, and is heated at a frequency of 13.56 MHz from a high frequency power source (739) while the gas flow rate and pressure are stable. Applying 35 Watts of power to the power application electrode (736),
Generated a glow discharge. This discharge was performed 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 24 at% of the total constituent atoms, and the boron atoms were 10 at ppI.
Th fluorine atom is 5 at%, germanium atom is 10.5
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 -590V (+590V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 39 V/.mu.m (39 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for the surface potential to decay from Vmax to 90% of Vmax in the dark is approximately 14 seconds (approximately 13 seconds), which indicates that it has sufficient charge retention performance. I completely understood. 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 band III, and the required light amount was 1.5.
lux·sec (1.4 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 addition, after initial charging to the highest charging potential, a semiconductor laser beam (emission wavelength 780 nm) was used to charge the 2nd layer at the 41st highest band.
When light was attenuated to 0% surface potential, the amount of light required was 9.8 erg/cm2 (8.0erg/cm2).
From this, it was understood that it has sufficient long-wavelength photosensitivity performance.

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. 7, first, the reaction bag f! After making the inside of (733) a high vacuum of about 10-6 Torr, the first, second, third, and fourth control valves (
707, 708, 709, and 710), and
Hydrogen gas from tank (701), second tank (702)
Butadiene gas, carbon dioxide gas from the third tank (703), and carbon tetrafluoride gas from the fourth tank (704) were supplied to the first, second, and second tanks under an output pressure of 1.0 Kg/cm2, respectively.
Third and fourth flow controllers (713, 714, 715,
and 716). Then, adjust the scales of each flow rate controller to set the flow rate of hydrogen gas to 60 seconds, the flow rate of butadiene gas to 60 sccm, the flow rate of carbon dioxide gas to 12 seconds, and the flow rate of carbon tetrafluoride gas to 160 seconds.
ecm, and flowed into the reaction chamber (733) from the main pipe (732) via an intermediate mixer (731).

After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 1.6 Torr. On the other hand, as the conductive substrate (752), fir 5
Using an aluminum substrate of 0x width 50x thickness 3mm, heat it in advance to 120°C, and with the gas flow rate and pressure stable, connect the low frequency power supply (741) with the connection selection switch (744) in advance. ) and apply 130W of power to the power application electrode (736) at a frequency of 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 the amount of hydrogen atoms contained was 51 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, that is, fluorine atoms, was 18.0 at% based on the total constituent atoms, and the amount of oxygen atoms was 2.0 at% based on the total constituent atoms.

Charge generation layer forming step: Next, some tanks are replaced and the first FI control valve (707)
, the second control valve (708), the third control 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). At the same time, the fourth control valve (710) is opened, and phosphine gas diluted to 1100 pp with hydrogen gas is supplied from the fourth tank (704) to the fourth tank under an output pressure of 1°5 Kg/cm2.
It was made to flow into the flow rate controller (716). Adjust the scale of each flow fil# control to set the hydrogen gas flow rate to 200 sec.
The flow rate of the germane gas was set to 6 s e cm The flow rate of the N tetrafluorosilane gas was set to 50 S CCmz The flow rate of the silane gas was 50 sec 1 The flow rate of the phosphine gas diluted to 1100 pp with hydrogen gas was set to 10105e, and the reaction chamber (
733). After each flow rate stabilizes,
The pressure regulating valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 0.8 Torr.

On the other hand, a conductive substrate (752) on which an a-C film is formed
is heated to 240°C, and when the gas flow rate and pressure are stable, the frequency is 13.5 from the high frequency power supply (739).
40Watt to the power application electrode (736) under 6MHz
electric power was applied to generate a glow discharge. This discharge was performed for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-SiN 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 26 atomic% and the phosphorus atoms were 13 atomic ppm% of the total constituent atoms.
The content of fluorine atoms was 5.6 at%, and the content of germanium atoms was 9.8 at%.

Characteristics: When the obtained photoreceptor was used in a conventional Carlson process with both negative and positive charging, the following -1 was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -250V (+340V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was as high as 16 .mu.m/.mu.m (22 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance. In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 5 seconds, which indicates that it has sufficient charge retention performance. Ta. Furthermore, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential, and the amount of light required was 3.4 lux sec (5. ), and from this it can be understood 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.

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

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. and the fourth control valve (7
07, 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 oxygen gas from the fourth tank (704). The first, second, third, and fourth flow rate controllers (713, 714, 715, and 71
6) Allowed to flow into the interior. Then, adjust the scales of each flow rate controller to set the flow rate of hydrogen gas to 180 sec, the flow rate of butadiene gas to 40 sec, and the flow rate of oxygen gas to 4 sec.
The flow rates of Crrh and carbon tetrafluoride gas are set to 10105e, 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 control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 2.0 Torr. On the other hand, the conductive substrate (752) is
Using an aluminum substrate measuring 50 mm in width and 3 mm in thickness, it was preheated to 180°C, and with the gas flow rate and pressure stable, it was connected to a low frequency power source (741) using the connection selection switch (744). ) and apply 200 Watt (7) power to the power application electrode (736) at a frequency of 600.
A plasma polymerization reaction was performed for about 30 minutes by applying a voltage of KHz (7), and a 15 μm thick a
-C film was formed as a charge transport layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 40 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, that is, fluorine atoms, was 4.1 at% based on the total constituent atoms, and the amount of oxygen atoms was 1.8 at% based on the total constituent atoms.

Charge generation layer forming step: Next, in the same manner as in Example 1, a charge generation layer of a photoreceptor according to the present invention was formed.

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 -520V (+490V), 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 .mu.m/.mu.m (32 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 13 seconds (approximately 12 seconds).
seconds), and from this it was reasonable to have 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 2.6 lux · seconds (1.2 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.

[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 7 Figure Z Figure 4 “ Figure 6 Procedural Amendments 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 photoreceptor characterized by being a hydrogenated amorphous silicon germanium film containing at least one of atoms and boron atoms, or a fluorinated amorphous silicon germanium film containing at least one of phosphorus atoms and boron atoms. .