JPS6382461A - 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 alkali metal 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 oxygen and alkali metal. 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.

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

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

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

In order to overcome these drawbacks, in recent years, amorphous silicon, which can be produced by a glow discharge method, has been increasingly applied to electrophotographic photoreceptors as a material with improved toxicity and increased durability. However, while amorphous silicon requires a large amount of silane gas as a raw material, it is an expensive gas, so the resulting electrophotographic photoreceptor is also significantly more expensive than a conventional photoreceptor. In addition, there are many inconveniences in production, such as the slow film formation rate and the generation of explosive silane undecomposed products in the form of dust as the film formation time increases. Furthermore, if this dust gets mixed into the photosensitive layer during manufacturing, it will have a significant negative effect on image quality. Furthermore, since amorphous silicon originally has a high dielectric constant, it has poor charging performance, and in order to charge it to a predetermined surface potential in a copying machine, it is necessary to increase the thickness of the film. It has to be deposited.

By the way, amorphous carbon M'A 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 Poly
The film formability is also discussed in the field of merization.

However, plasma organic polymer films prepared by conventional methods are used only for applications that assume insulation properties, that is, these films have a resistance of less than 10'6 Ωcm like ordinary polyethylene films.
It was considered to be an insulating film having a certain specific resistance, or at least was used with the recognition that it was such a film. 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 1016 Ωcm generated from a mixed gas of oxygen, nitrogen, and hydrocarbon is provided on a substrate as a blocking layer and an adhesive layer by 10 to 100 people. A photoreceptor is disclosed that includes an amorphous silicon layer. Unexamined Japanese Patent Publication 1987-
Publication No. 136742 discloses a photoreceptor in which a carbon film of approximately 1 to 5 μm is formed on the surface of the substrate as a protective layer to prevent aluminum atoms from diffusing into the amorphous silicon layer provided on the aluminum substrate during light irradiation. has been fully disclosed.

Japanese Unexamined Patent Publication No. 60-63541 discloses a photosensitive material in which a diamond-like carbon film with a thickness of 200 to 2 μm is provided in the middle as an adhesive layer in order to improve the adhesion between an aluminum substrate and an amorphous silicon layer provided thereon. It is said that the film thickness is preferably 2 um 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-St
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-60-61761 discloses a photoreceptor provided with a diamond-like carbon thin film of 500A to 2 μm as a surface protective layer, and it is said that the film thickness is preferably 2 μm or less from the viewpoint of light transmission. There is.

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

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

Philosophical Magazine (Philosophical Magazine) published in 1976 by
Magazine) Volume 33, pages 935 to 94
Since it was reported on page 9 that it is a material that can control polarity, attempts have been made to apply it to various charging 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, plasma organic polymer films conventionally used in electrophotographic photoreceptors have been used as so-called undercoat layers or overcoat layers; It is a film that does not require a transport function, and is used based on the judgment that the organic polymer film is insulating.Therefore, it is only used as an extremely thin film with a thickness of about 5 μm at most, and the carriers are tunneled. If the tunneling effect cannot be expected, it is only used with thin films that are virtually free of problems regarding the generation of residual potential. The amorphous silicon film used is a so-called thick film, and has many disadvantages in terms of cost, productivity, etc.

While considering the application of amorphous carbon films to electrophotographic photoreceptors, the present inventors discovered that hydrogenated amorphous carbon films, which were originally thought to be insulating, were able to absorb oxygen atoms and alkali metal atoms. It has been found that by containing it, when laminated with a hydrogenated or fluorinated amorphous silicon germanium film, it has charge transport properties and easily begins to exhibit suitable electrophotographic properties. Although the theoretical interpretation has many unclear points even for the present inventors, it is not possible to discuss it in detail. The band structure formed by electrons in stable energy states, such as π electrons, unpaired electrons, and residual free radicals, is similar to the band structure formed by hydrogenated or fluorinated amorphous silicon germanium in the conduction band or valence band. Because of the energy level, carriers generated in the hydrogenated or fluorinated amorphous silicon germanium film can be easily injected into the hydrogenated amorphous carbon film containing oxygen atoms and alkali metal atoms. It is presumed that this is because the electrons can travel suitably through the hydrogenated amorphous carbon film containing oxygen atoms and alkali metal atoms due to the action of the electrons in the relatively unstable energy state mentioned 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 To provide a photoreceptor using a hydrogenated amorphous carbon film containing atoms and alkali metal atoms as a charge transport layer and a thin film of hydrogenated or fluorinated amorphous silicon germanium as a charge generation layer. With the goal.

for the purpose of

That is, the present invention provides a functionally separated photoreceptor having a charge generation layer and a charge transport layer, in which the charge transport layer contains at least oxygen atoms and alkali metal atoms produced by a plasma polymerization reaction. It relates to a photoreceptor characterized in that it is an amorphous carbon film and the charge generation layer is hydrogenated or fluorinated amorphous silicon germanium (hereinafter, the charge transport layer according to the present invention is referred to as a-C).
The film and charge generation layer are referred to as a-Si films).

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

That is, the present invention provides a hydrogenated amorphous carbon film containing at least oxygen atoms and alkali metal atoms that can be generated by glow discharge as a charge transport layer, and a hydrogenated amorphous carbon film that can also be generated by glow discharge as a charge generation layer. Alternatively, the present invention relates to a functionally separated photoreceptor characterized by being provided with a 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 is also excellent in light transmittance, an extremely high degree of freedom can be obtained when forming a laminated structure as a functionally separated photoreceptor. In addition, the charge generation layer has excellent photoconductivity for visible light or light with a wavelength near semiconductor laser light, and has an extremely thin film thickness compared to conventional amorphous silicon photoreceptors. It is something that can be put to good use.

In the present invention, an organic compound gas, particularly a hydrocarbon gas, is used to form the a-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, bebutadiene, 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, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, etc. and cycloolefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, limonene, tervirune, phellandrene, sylvestrene, thuen, carene, pinene, bornylene, camphuene, fuenchen , cycloundecane, tricyclene, bisabolene, zingiberene, curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, campholene, phylloclatene, bodocarbrene, mirene, and other terpenes, steroids, and the like are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, pseudocumene, mesitylene, prenitene, isodurene, durene,
Pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, piphenyl, terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

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

The amount of hydrogen atoms contained in a-C1g in the present invention is inevitably determined from the manufacturing aspect of using glow discharge, but is approximately 36% of the total amount of carbon atoms and hydrogen atoms.
It is contained in an amount of 60 atomic %. Here, the content of carbon atoms and hydrogen atoms in the film is determined using a conventional method for organic elemental analysis, for example, C
This can be determined by using NH 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, raising 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 film thickness of a-CPJ as a charge transport layer in the present invention is suitably 5 to 50 μm and 7 to 20 μm for use in a normal electrophotographic process, and if it is thinner than 5 μm, the charging potential is low. It is not possible to obtain sufficient copy image density. Moreover, if it is thicker than 50 μm, it is not preferable in terms of productivity.

This a-C film has light transmittance, dark resistance, and is rich in charge transport properties.As mentioned above, even if the film thickness is 5 μm or more, carriers are transported without being trapped and contribute to bright attenuation. It 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 method, ion beam vapor deposition method, etc., or neutral state produced by vacuum vapor deposition method, sputtering method, etc. It may be formed from particles 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,
Inorganic compounds such as carbon suboxide, hydroxyl groups (-OH), aldehyde groups (-COH), acyl groups (RCO-, -CR
O), ketone group (>Co), ether bond (-〇-)
, ester bond (-Coo-), heterocycle containing oxygen,
An organic compound having a functional group or bond such as the like is used. As the organic compound having a hydroxyl group, for example, methanol, ethanol, propatool, butanol, furyl alcohol, fluoroethanol, fluorobutanol, phenol, cyclohexanol, benzyl alcohol, furfuryl alcohol, etc. are used. Examples of 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, salicylic acid, cinnamic 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, methylhebutenone, cyclobutanone, cyclopentanone, cyclohexanone, Acetophenone, propiophenone, butyrophenone, valerophenone, dibenzyl ketone, acetonaphthone, acetochenone, acetofuron, etc. are used. Examples of organic compounds having an ether bond include methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, ethyl methyl ether, methyl propyl ether, methyl butyl ether, methyl amyl ether, ethyl propyl ether, ethyl butyl ether, and ethyl amyl ether. , vinyl ether, allyl ether, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, ethylfuryl ether, anisole, phenetol, phenyl ether, benzyl ether, phenylbenzyl ether, naphthyl ether, ethylene oxide, propylene oxide, trimethylene oxide,
Tetrahydrofuran, tetrahydrobilane, dioxane, etc. are used. Examples of organic compounds having an ester bond include methyl formate, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl propionate, ethyl propionate, and propion. propyl acid, butyl propionate, amyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, amyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, amyl valerate, methyl benzoate, Ethyl benzoate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, methyl salicylate, ethyl salicylate, propyl salicylate, butyl salicylate, amyl salicylate,
Methyl anthranilate, ethyl anthranilate, butyl anthranilate, amyl anthranilate, methyl phthalate, ethyl phthalate, butyl phthalate, and the like are used. Examples of heterocyclic compounds containing oxygen include furan, oxazole, furazane, biran, oxazine, morpholine, benzofuran, pandioxazole, chromene, chroman, dibenzofuran, xanthine, phenoxazine, oxolane, dioxolane, oxathiolane, oxadiazine, benzisoxazole, etc. is used.

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

In the present invention, the amount of oxygen atoms contained as a chemical modifier can be controlled mainly by increasing or decreasing the amount of the aforementioned oxygen compound introduced into the reaction chamber in which the plasma reaction is performed. If the amount of oxygen compound introduced is increased,
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, it is possible to increase the amount of oxygen atoms added to the acvc film according to the present invention. It is possible to lower it.

In the present invention, in addition to hydrocarbons, an alkali metal compound is used to add at least alkali metal atoms into the a-C film. Here, the alkali metal atom refers to a lithium atom, a sodium atom, a potassium atom, a rubidium atom, and a cesium atom. The phase state of the alkali metal compound gas does not necessarily have to be a gas phase at room temperature and normal pressure; in fact, since there are few compounds in a gas phase, it can be melted, evaporated, sublimated, etc. by heating or reduced pressure, etc. It can be used in either liquid phase or solid phase as long as it can be converted into a liquid phase. As the alkali metal compound, for example, metal alcoholade, metal acrylic acid, metal methacrylic acid, metal phthalocyanine, etc. can be used.

In the present invention, the amount of alkali metal atoms contained as a chemical modifier is 0.1 to 10
% by atom, preferably from 0.3 to 5 atomic%. Here, the content of alkali metal atoms in the film can be determined by a conventional method of elemental analysis, such as Auger analysis. If the amount of alkali metal atoms is lower than 0°1 at%, 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 guaranteed. It will no longer be done. When the amount of alkali metal atoms is higher than 10 atomic %, the alkali metal atoms which, when added in an appropriate amount, ensure suitable charge transport properties and prevention of residual potential generation, conversely cause a decrease in charging ability. Furthermore, film-forming properties are not necessarily guaranteed, and the film is likely to peel off, become oily, or turn into powder.

Therefore, the range of the amount of alkali metal atoms added in the present invention is important.

In the present invention, the amount of alkali metal atoms that can be contained as a chemical modifier can be controlled mainly by increasing or decreasing the amount of the alkali metal compound introduced into the reaction chamber in which the plasma reaction is performed. By increasing the amount of alkali metal compound introduced, it is possible to reduce the amount of alkali metal atoms added to the a-C film according to the present invention, and conversely, it is possible to decrease the amount of alkali metal compound introduced. For example, it is possible to reduce the amount of alkali metal atoms added to the a-C film according to the present invention.

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

The content of germanium atoms contained in the a-Si film in the present invention is preferably 30 at % or less with respect to the total of silicon atoms and germanium atoms. Here, the contents of germanium atoms and silicon atoms can be determined by a conventional method of elemental analysis, for example, Auger analysis. The content of germanium atoms can be increased by increasing the flow rate of germane gas flowing during film formation. As the content of germanium atoms increases, the long-wavelength sensitivity of the photoreceptor of the present invention improves, and a wide range of exposure sources can be selected from the short wavelength region to the long wavelength region, which is preferable. Excessive addition is not preferable since a large content will lead to a decrease in charging ability. Therefore, the content of germanium atoms contained in the a-3i film in the present invention is important.

The amount of hydrogen atoms or fluorine atoms contained in the a-5i model of the present invention is necessarily determined from the manufacturing aspect of using glow discharge, but the total amount of silicon atoms and hydrogen atoms or silicon atoms and fluorine atoms On the other hand, the content is approximately 10 to 35 at%. Here, the content of hydrogen atoms or fluorine atoms in the film can be determined by using conventional methods of elemental analysis, such as ONH analysis and Auger analysis. .

The appropriate thickness of the a-3i film as the charge generation layer in the present invention is 0.1 to 5 μm for use in a normal electrophotographic process, and if it is thinner than 0.1 μm, light absorption is insufficient. As a result, sufficient charge generation is not performed, resulting in a decrease in sensitivity. Moreover, if it is thicker than 5 μm, it is not preferable in terms of productivity. This a-Si film has a rich charge generation ability,
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-3i 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.

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 one form of the method, in which a charge transport layer (2) and a charge generation JW (3) are sequentially deposited on a conductive substrate (1) by WIL,
, shows the configuration. 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 a conductive substrate (1) as another form.
The top shows a structure in which a charge transport layer (2), a charge generation H (3), and a charge transport layer (2) are sequentially laminated.

When the surface of the photoreceptor is positively charged with, for example, a corona charger, and then used for image exposure, the holes generated in the charge generation FJ (3) in FIG.
) in the direction towards the conductive substrate (1), and in Figure 2, electrons generated in the charge generation layer (3) travel in the charge transport N (2) towards the surface of the photoreceptor; In this case, holes generated in the charge generation layer (3) travel toward the conductive substrate (1) through the charge transport layer (2) on the conductive substrate side, and at the same time, electrons generated in the charge generation layer (3) travel toward the conductive substrate (1). travels through the charge transport layer (2) on the front side toward the photoreceptor surface, forming an electrostatic latent image with proper brightness attenuation. On the other hand, when the surface of the photoreceptor is negatively charged and then used for image exposure, the behavior of electrons and holes can be exchanged to understand the mobility of carriers. In FIGS. 2 and 3, the irradiation light for image exposure passes through the charge transport layer, but since the charge transport layer according to the present invention has excellent translucency, it forms a suitable latent image. Is possible.

FIG. 4 shows, 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, since the outermost surface is an n-C film with excellent durability, there is no need to provide a surface protective layer.
For example, a surface protective layer may be provided for the purpose of adjusting the compatibility with various elements within the copying machine, such as preventing staining of the surface of the photoreceptor due to adhesion of developer.

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 a further 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-σ 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 has an electrode heating M
(737) allows for heating. A high frequency power supply (739) and a low frequency power matching box (74) are connected to the power applying electrode (736) via a matching box for high frequency power (738).
A low-frequency power source (741) is connected to the low-frequency power source (741) through a low-pass filter (742), and a DC N source (743) is connected to the low-frequency power source (743) through a low-frequency power source (741), and power with different frequencies can be applied using 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), an oil rotary Pump (74'8
), or by a cooling exclusion device (749), a mechanical booster pump (750), or an oil rotary pump (748). The exhaust gas is further rendered safe and harmless by an appropriate exclusion device (753) before being exhausted into the atmosphere. These exhaust system piping can also be heated by appropriately placed piping heaters (734) to prevent the vaporized gas of the raw material compound, which is in a liquid or solid phase state at room temperature, from condensing on the way. ing. Reaction chamber (7
33) can also be heated by the reaction chamber heater (751) for the same reason, and a conductive substrate (
752) can be installed. In FIG. 7, a conductive substrate (7
52) is fixed to the ground electrode (735), but may be fixed to the power application electrode (736),
Furthermore, they may be placed 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 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 rate using the first to ninth flow rate controllers, and the inside of the reaction chamber is kept constant using the pressure control valve. Maintain a reduced pressure. After the gas flow rate is stabilized, a connection selection switch is used to select, for example, a high frequency power source, and high frequency power is applied to the power application electrode.

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

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

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Valve (707,
708 and 709), and the first tank (701)
hydrogen gas, ethylene gas from the second tank (702), and oxygen gas from the third tank (703) are supplied to the first, second, and third flow rate controllers (713) under an output pressure of 1.0 Kg/cm2, respectively. , 714, and 715).

At the same time, potassium methacrylate (K-MA) gas is supplied from the second container (720) to the second temperature controller (723) at a temperature of 190.
℃ into the eighth flow rate controller (729).

Adjust the scale of each 'tC amount controller to set the hydrogen gas flow rate to 70 sec and the ethylene gas flow rate to 70 sec.
s Set the flow rate of oxygen gas to 4 seconds and the flow rate of potassium methacrylate gas to 8 seconds,
It flowed into the reaction chamber (733) from the main pipe (732) via an intermediate mixer (731). After each flow rate stabilized, the pressure inside the reaction chamber (733) was 2.2T.

The pressure regulating valve (745) was adjusted so that rr. On the other hand, as a conductive substrate (752), tji5o x horizontal 5
Using an aluminum substrate with a thickness of 0 x 3 mm, 230
℃, and with the gas flow rate and pressure stable, turn on the high frequency power source (739) that was previously connected using the connection selection switch (744), and connect the power application electrode (73).
6) 220Watt power at frequency 13.56MHz
A plasma polymerization reaction was carried out for about 3 hours under the following conditions, and a 15 μm thick a-C film was formed 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.

When organic elemental analysis was performed on the a-C film obtained as described above, the amount of hydrogen atoms contained was 43 at % based on the total amount of carbon atoms and hydrogen atoms. Further, according to Auger analysis, the amount of alkali metal atoms, ie, potassium atoms, that could be contained was 0.6 at % based on the total constituent atoms. Further, the content of oxygen atoms was 1.1 at % based on all 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 hydrogen gas flow rate to 200 sec, the germane gas flow rate to 20 sec, and the silane gas flow rate to 101005 sec.
e to flow into the reaction chamber (733). After each flow rate stabilizes, the pressure in the reaction chamber (733) decreases to 1.
The pressure control valve (745) was adjusted so that the pressure was 0 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).
45W to the 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 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 -370V (+420V), 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 24 V/.mu.m (27 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 9 seconds (approximately 11 seconds), which indicates that it has sufficient charge retention performance. Ta. In addition, after initial charging to the highest charging potential,
When white light was used to brightly attenuate the surface potential to 20% of the highest charging potential, the amount of light required was 1.8 lux·sec (2°1 lux·sec), which indicates that there is sufficient light. It was understood that it has 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.

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. 707,70
8, and 709), hydrogen gas from the first tank (701), butadiene gas from the second tank (702),
and oxygen gas from the third tank (703) at an output pressure of 1
．． It was allowed to flow into the first, second, and third flow controllers (713, 714, and 715) under 0 Kg/cm2.

At the same time, lithium tertiary is supplied from the second container (720).
Butirad gas was made to flow into the eighth flow rate regulator (729) with the temperature of the second temperature regulator (723) at 190°C. Adjust the scale of each flow controller to set the hydrogen gas flow rate to 70
sec, the flow rate of butadiene gas is set to 70 sec, the flow rate of oxygen gas is 4 scCm, and the flow rate of lithium tertiary-butylade gas is set to 8 sec, and the flow rate is set to 8 sec, and the flow rate is set to 8 sec. (733) flowed into the interior. After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 2.2 Torr. On the other hand, the conductive substrate (752) is 50 mm x 50 mm x 3 mm thick.
Using an aluminum substrate, heat it in advance to 150°C, and with the gas flow rate and pressure stable, turn on the low frequency power supply (741) that was previously connected with the connection selection switch (744), and turn on the power. 150 to the application electrode (736)
Watt's power was applied at a frequency of 600 KHz to carry out a plasma polymerization reaction for about 45 minutes, and the conductive substrate (75
2) 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.

When the a-CM obtained as described above was subjected to an organic elemental analysis tank, the amount of hydrogen atoms contained was 53 at % based on the total amount of carbon atoms and hydrogen atoms. Further, according to Auger analysis, the amount of alkali metal atoms, ie, lithium atoms, contained was 1.7 at % based on the total constituent atoms. Further, the content of oxygen atoms was 0.8 at % based on all 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 (703) and the sixth
Silane gas is supplied from the tank (706) at an output pressure of IKg/c.
The first, second, third, and sixth flow controllers (7
13,714,715, and 718).

Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200.
sec cm, the flow rate of the silane tetrafluoride gas to 50 sec, the flow rate of the germane gas to 6 sec cm, and the flow rate of the silane gas to 50 sec cm, and the flow rate was made 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.

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 18 at% and the fluorine atoms were 18 at% based on the total constituent atoms. The content of germanium atoms was 5 at%, and the content of germanium atoms was 11 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 -490V (+600V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 32 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 dark decay from Vmax to 90% of Vmax in the dark was approximately 11 seconds (approximately 15 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated using white light to a surface potential of 20% of the highest charging potential, and the amount of light required was 1.3 lux · seconds (1.8 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 (emission wavelength: 780 nm)? ,8e
rg/cm2 (11,2 erg/cm2), and from this it was understood that it had sufficient long wavelength light sensitivity performance.

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

When an image was formed and transferred to this photoreceptor using the commonly used Carsilan process, a clear image was obtained.

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

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Valve (707,70
8, and 709), hydrogen gas from the first tank (701), acetylene gas from the second tank (702),
Carbon dioxide gas was flowed from the third tank (703) into the first, second, and third flow rate controllers (713, 714, and 715) under an output pressure of 1°0 Kg/cm 2 . At the same time, lithium tert-butyrad gas is supplied from the second container (720) to the second temperature controller (723) at a temperature of 220.
℃ into the eighth flow rate controller (729).

Adjust the scale of each flow rate side meter to set the hydrogen gas flow rate to 200 sec and the acetylene gas flow rate to 50 sec.
The flow rate of carbon oxide gas is set to 10105e, and the flow rate of lithium tertiary-butylade gas is set to 18 seconds. (732) 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 2.5 Torr. On the other hand, the conductive substrate (752) is
A high-frequency power source (739) using an aluminum substrate measuring 50 mm wide x 3 mm thick, preheated to 220°C, and connected with a connection selection switch (744) while the gas flow rate and pressure are stable. and applied a power of 220 Watts to the power application electrode (736) at a frequency of 13.56
Plasma polymerization reaction was carried out for about 2 hours and 15 minutes by applying the voltage under MHz, 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.

When the a-Chi obtained as described above was subjected to organic elemental analysis, the amount of hydrogen atoms contained was 33 at % based on the total amount of carbon atoms and hydrogen atoms. Also,
Based on Auger analysis, the alkali metal atoms contained, i.e.
The amount of lithium atoms was 3.4 at% based on the total constituent atoms. Further, the content of oxygen atoms was 0.9 at % based on all 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 flowed inside. 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 10100 sec.
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, a conductive substrate (
752) was heated to 250°C, and with the gas flow rate and pressure stable, a power of 35 Watt was applied to the TiJN (736) at a frequency of 13.56 MHz from the high frequency power source (739), and a glow was generated. caused an electrical discharge. This discharge was performed 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 ○NH analysis in metal (Full EMGA-1300 manufactured by Itaba) and Auger analysis, it was found that the hydrogen atoms contained were 2 to 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 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 (+630V), 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 V/.mu.m (41 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 12 seconds (approximately 16 seconds).
seconds), and from this we can understand that it has sufficient charge retention performance. Furthermore, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential, and the amount of light required was 1.3 lux·sec (1, flux·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), and the amount of light required was 8. le
rg/cm2 (9.2 erg/cm2), and from this it was understood that it had sufficient long wavelength light sensitivity performance.

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

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

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

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. 707,70
8, and 709), hydrogen gas from the first tank (701), butadiene gas from the second tank (702),
and oxygen gas from the third tank (703) at an output pressure of 1
．． It was allowed to flow into the first, second, and third flow controllers (713, 714, and 715) under 0 Kg/cm2.

At the same time, potassium methacrylate (K-MA) gas is supplied from the second container (720) to the second temperature controller (723) at a temperature of 260.
℃ into the eighth flow rate controller (729).

Adjust the scale of each flow rate side @ FA to FA, and set the hydrogen gas flow rate to 120 sec and the butadiene gas flow rate to 50 sec.
The flow rate of ms oxygen gas was set to 6 sec, and the flow rate of potassium methacrylate gas was set to 5 sec, and the gas 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 inside the reaction chamber (733) was 2.2 Torr. On the other hand, the conductive substrate (752) is 50 mm x 50 mm x 3 mm thick.
Using an aluminum substrate, heat it in advance to 230°C, and with the gas flow rate and pressure stable, turn on the low frequency power supply (741) that was previously connected with the connection selection switch (744), and turn on the power. 170 to the application electrode (736)
Watt's power was applied at a frequency of 800 KHz to perform a plasma polymerization reaction for about 1 hour and 30 minutes, and the conductive substrate (
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 of the a-C film obtained as described above revealed that the amount of hydrogen atoms contained was 41 at % based on the total amount of carbon atoms and hydrogen atoms. Further, according to Auger analysis, the amount of alkali metal atoms, ie, potassium atoms, contained was 0.9 at % based on the total constituent atoms. Further, the content of oxygen atoms was 1.8 at % based on all 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/am2.
, 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 hydrogen gas flow rate to 200sec, the germane gas flow rate to 2secms, and the silane gas flow rate to 11005CC.
was set to flow into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 0.8
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).
．． 35W to the power application electrode (736) under 56MHz
A glow discharge was generated by applying a power of tt.

This discharge was performed 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 -630V (+780V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 41 V/.mu.m (51 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 22 seconds (approximately 27 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 2.3 lux·sec (2.9 lux·sec). seconds), and from this it is clear that it has sufficient photosensitivity performance! E finished.

From the above, it can be concluded 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 clearly provided.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. , and 7
09), hydrogen gas is released from the first tank (701),
and the third tank (T.

3) Oxygen gas was caused to flow into the first and third flow rate controllers (713 and 715) under an output pressure of 1.0 Kg/cm2. At the same time, styrene gas is supplied from the first container (719) to the seventh temperature controller (722) at a temperature of 40°C.
into the flow controller (728) and into the second container (720
), the lithium tertiary-butylade gas was supplied to the second temperature controller (723) at a temperature of 170°C, and then passed to the eighth flow rate controller (723).
29) It was allowed to flow into the interior. FA the scale of each flow controller
The flow rate of hydrogen gas is 70 seconds, the flow rate of styrene gas is 40 seconds, and the flow rate of oxygen gas is 10105e.
, and the flow rate of lithium tert-butylade gas to 8
secm, and mixer (731)
It flowed into the reaction chamber (733) from the main pipe (732) through the main pipe (732). After each flow rate is stabilized, the reaction chamber (733)
Pressure regulating valve (7) so that the internal pressure is 2°2 Torr.
45) was adjusted. On the other hand, as the conductive substrate (752), use an aluminum substrate of 50 mm x 50 mm x 3 mm in thickness, heat it to 90°C in advance, and when the gas flow rate and pressure are stable, use the connection selection switch (744). ) is connected to the low frequency power source (741), and a power of 150 Watt is applied to the power application electrode (736) at frequency 5.
The plasma polymerization reaction was carried out for about 45 minutes by applying a voltage of 0 KHz, and a 15-um-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.

When the a-C film obtained as described above was subjected to organic elemental analysis, the amount of hydrogen atoms contained was 47 at % based on the total amount of carbon atoms and hydrogen atoms. Further, according to Auger analysis, the amount of alkali metal atoms, ie, lithium atoms, contained was 1.7 at % based on the total constituent atoms. Further, the content of oxygen atoms was 2.1 at % based on all 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 IIIm units (713, 714, and 718). Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 200 seconds, germane gas flow rate to 6 seconds, and silane gas flow rate to 10100 seconds.
5e and flowed into the reaction chamber (733). After each flow rate stabilizes, the pressure in the reaction chamber (733) becomes 0.
．． The pressure control valve (745) was adjusted to 9 Torr. On the other hand, a conductive substrate (
752) is heated to 250°C, and with the gas flow rate and pressure stable, a high frequency power source (739) applies power to the electrode (736) at a frequency of 13.56 MHz at 40°C.
Watt power 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 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 -370V (+540V), 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 24 V/.mu.m (35 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 7 seconds (approximately 14 seconds), which clearly indicates that it has sufficient charge retention performance. Ta. In addition, after initial charging to the highest charging potential,
When white light was used to brightly attenuate the surface potential to 20% of the highest charging potential, the amount of light required was 1.1 lux·sec (1°5 lux·sec), which indicates that there is sufficient light. It was understood that it has sensitivity performance. In addition, after initial charging to the highest charging potential, semiconductor laser light (emission wavelength 7
The light intensity required to achieve brightness attenuation to a surface potential of 20% of the highest charging potential was 6.8er.
g/am2 (8.3 erg/cm2), and from this it was understood that it had sufficient long wavelength light sensitivity performance.

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

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

[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 dated 21st JO, 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 alkali metal atoms; A photoreceptor characterized by being a hydrogenated or fluorinated amorphous silicon germanium film.