JPS6382438A - Photosensitive body - Google Patents

Abstract

PURPOSE:To form a photosensitive layer which has excellent photosensitive characteristics and is extremely thin in film thickness by forming an electric charge transfer layer of a hydrogenated amorphous carbon film contg. oxygen and alkali metal atoms and an electric charge generating layer of a hydrogenated or fluorinated amorphous silicon film contg. at least either of phosphorus or boron atoms, respectively. CONSTITUTION:The charge transfer layer 2 of a function sepn. type photosensitive body having the charge transfer layer 2 and the charge generating layer 3 is formed of the hydrogenated amorphous a-C film which is formed by glow discharge and contains the oxygen atoms and the alkali metal atoms and the charge generating layer is formed of the hydrogenated or fluorinated amorphous silicon a-Si film which contains at least either of the phosphorus atoms or boron atoms. The content of H in the a-C film is specified to 30-60% of the total content of C and H and the content of the oxygen to <=7% and the content of the alkali metal to 0.1-10%. The content of the phosphorus or boron in the a-Si film is specified to <=20,000ppm. The charge transfer layer 2 is thereby improved in transferability, electric chargeability, durability and translucency, and the charge generating layer 3 is provided with the excellent photoconductivity of visible light and wavelength light near laser light and is extremely reduced in the film thickness.

Description

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

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

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

However, the electrophotographic photoreceptor materials conventionally used each have drawbacks. One of these is its toxicity to the human body, and all inorganic substances other than the amorphous silicon described 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.

Amorphous carbon films themselves have long been known as plasma organic polymerized films, such as diene (M, 5he
Journal of Applied Polymer Science, published in 1973 by J.
In vol. 17, pages 885 to 892 of Lied Polymer Science, the same author also states that it can be made from gases of any organic compound.
American Chemical Society (Ame) in 1979
rican Cem1ca I Soc 1ety)
sma Polymerization), its film formability is also discussed.

However, plasma organic polymer films prepared by conventional methods are used only for applications that require insulation, that is, they are considered to be insulating films with a specific resistance of about <1016 Ωam, 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-
Publication No. 136742 discloses a photoreceptor in which a carbon film of approximately 1 to 5 μm is formed on the surface of the substrate as a protective layer to prevent aluminum atoms from diffusing into the amorphous silicon layer provided on the aluminum substrate during light irradiation. is disclosed.

Japanese Unexamined Patent Publication No. 60-63541 discloses a photosensitive material in which a diamond-like carbon film with a thickness of 200 to 2 μm is provided in the middle as an adhesive layer in order to improve the adhesion between an aluminum substrate and an amorphous silicon layer provided thereon. It is said that the film thickness is preferably 2 μm or less in terms of residual charge.

All of these disclosures are inventions in which a so-called undercoat layer is provided between the substrate and the amorphous silicon layer,
There is no disclosure regarding charge transport properties, and a-3i
However, it does not solve the above-mentioned essential problems.

For example, Japanese Patent Application Laid-Open No. 50-20728 discloses that a polymer film of 0.1 to 1 μm formed by glow discharge polymerization is applied as a protective layer on the surface of a polyvinylcarbazole-selenium photoreceptor.
A photoreceptor is disclosed. Japanese Patent Publication No. 59-214
No. 859 discloses that the surface of an amorphous silicon photoreceptor is A technique has been disclosed in which a film of about 5 μm is formed by plasma polymerizing organic hydrocarbon monomers such as styrene and acetylene as the J layer. Japanese Patent Publication No. 60-61761
The publication discloses a photoreceptor provided with a diamond-like carbon thin film of 500 to 2 .mu.m as a surface protective layer, and it is said that the film thickness is preferably 2 .mu.m or less from the viewpoint of light transmission. JP-A-60-249115 discloses that 0.05 to 5
A technique has been disclosed in which an amorphous carbon or hard carbon film with a thickness of about .mu.m is used as a surface protective layer, and it is said that if the film thickness exceeds 5 .mu.m, the photoreceptor activity is 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 about charge transport properties, and they do not solve the above-mentioned essential problems of a-Si. .

Further, JP-A No. 51-48130 discloses an electrophotographic photosensitive plate in which a polymer film of 0.001 to 3 μm is formed on the surface of a polyvinyl carbazole electrophotographic photoreceptor by glow discharge polymerization. However, there is no mention of charge transport properties, and it does not solve the above-mentioned essential problems of a-3i.

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

Philosophical Magazine 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, plasma organic polymer films conventionally used in electrophotographic photoreceptors have been used as so-called undercoat layers or overcoat layers, but they have a carrier transport function. This film is not necessary and is used based on the judgment that the organic polymer film is insulating. Therefore, it can only be used as an extremely thin film with a thickness of about 5 μm at most, and carriers either pass through the film by tunneling effect, or if a tunneling effect cannot be expected, there is virtually no interlayer in terms of residual potential generation. It is only used in thin films that can be used without any damage. 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, were able to absorb oxygen atoms and alkali metal atoms. By containing it, when laminated with a hydrogenated or fluorinated amorphous silicon 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 something. 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 film containing at least one of phosphorus atoms and boron atoms has a band structure formed by electrons in a stable energy state, such as π electrons, unpaired electrons, and residual free radicals. Since the formed band structure and the conduction band or valence band have similar energy levels, the carriers generated in the hydrogenated or fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms The carriers are easily injected into the hydrogenated amorphous carbon film containing oxygen atoms and alkaline earth atoms, and furthermore, these carriers are combined with oxygen atoms and alkali metal atoms by the action of the electrons in the relatively unstable energy state mentioned above. This is presumed to be due to the fact that the hydrogenated amorphous carbon film containing the hydrogenated amorphous carbon film can run suitably.

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 containing at least one of phosphorus atoms and boron atoms, using a hydrogenated amorphous carbon film containing atoms and alkali metal atoms as a charge transport layer. It is an object of the present invention to provide a photoreceptor using as a charge generation layer.

In other words, 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 generated from a plasma polymerization reaction. and the charge generation layer is a hydrogenated or fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms. Regarding a photoreceptor (hereinafter, the charge transport layer according to the present invention will be referred to as an a-C film and the charge generation layer will be referred to as an 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 alkali metal atoms produced by glow discharge as a charge transport layer, and a hydrogenated amorphous carbon film containing at least oxygen atoms and alkali metal atoms produced by glow discharge as a charge generation layer. The present invention relates to a functionally separated photoreceptor characterized by being provided with a hydrogenated or fluorinated amorphous silicon film containing at least one of phosphorus atoms and 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 excellent charging ability, durability, and weather resistance. It has excellent electrophotographic photoreceptor performance such as durability and environmental pollution resistance, and is also excellent in light transmission, so it provides an extremely high degree of freedom when forming a laminated structure as a function-separated photoreceptor. . Further, the charge generation layer has excellent photoconductivity with respect to visible light or light with a wavelength near semiconductor laser light,
Moreover, the film thickness is extremely thin compared to conventional amorphous silicon photoreceptors, and its functions can be fully utilized.

In the present invention, a-C1I! i! Organic compound gases, especially hydrocarbon gases, are used to form the .

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

There are many types of hydrocarbons that can be used, but examples of saturated hydrocarbons include methane, ethane, propane, butane,
Pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane,
tocosan, tricosane, tetracosan, pentacosan,
Normal paraffins such as hexacosane, heptacosane, octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, etc., as well as isobutane, isopentane, neopentane, isohexane, neohexane, 2,3-dimethylbutane, 2-methylhexane, 3- Ethylpentane, 2,2-dimethylpentane, 2
．． 4-dimethylpentane, 3,3-dimethylpentane,
Tributane, 2-methylhebutane, 3-methylhebutane, 2.2-dimethylhexane, 2.2.5-dimethylhexane, 2,2.3-trimethylpentane, 2.2.4
Isoparaffins such as -trimethylpentane, 2,3°3-trimethylpentane, 2,3.4-trimethylpentane, isonanone, etc. are used. Examples of unsaturated hydrocarbons include ethylene, propylene, isobutylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl -Olefins such as 2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-nonene, 1-decene, and allene, methylalene, butadiene, pentadiene, hexadiene,
Diolefins such as cyclopentadiene, triolefins such as ocimene, allocimene, myrcene, hexatriene, acetylene, butadiyne, etc.
゜3-pentadiyne, 2.4-hexadiyne, methylacetylene, 1-butyne, 2-butyne, 1-pentyne, 1
-Hexyne, 1-heptyne, 1-octyne, 1-nonine, 1-decyne, etc. are used.

Examples of alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloparaffins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, and cycloolefins such as limonene, tervirun, phelandrene, sylvestrene, thuene, carene, pinene, pornylene, camphuene, fuenchen , cycloundecane, tricyclene, bisabolene, zingiberene, curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, campholene, phylloclatene, bodocarprene, mirene, and other terpenes, as well as steroids, are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, 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 a-CN in the present invention is inevitably determined from the manufacturing aspect of using glow discharge, but it is generally contained in an amount of 30 to 6 atomic percent based on the total amount of carbon atoms and hydrogen atoms. . Here, the content of carbon atoms and hydrogen atoms in the film is determined using a conventional method for organic elemental analysis, for example, CNH
This can be known by using analysis.

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

The thickness of the a-C film as the charge transport layer in the present invention is 5 to 5
A suitable value is 0 μm, especially 7 to 20 ttm; if it is thinner than 5 μm, the charged potential will be low, making it impossible to obtain a 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 high light transmittance, high dark resistance, and is rich in charge transport properties, and even if the film thickness is 5 μm or more as mentioned above, carriers are transported without being trapped and contribute to bright attenuation. is possible.

The process of forming an a-C film from a raw material gas in the present invention is a method in which the raw material gas is formed through a plasma state that can be generated by a plasma method using direct current, low frequency, wave 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, an oxygen compound is used to add at least an oxygen atom to a-(JM. The phase state of the oxygen compound does not necessarily have to be a gas phase at room temperature and normal pressure. As long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure, it can be used in either liquid phase or solid phase.As oxygen compounds,
For example, inorganic compounds such as oxygen, ozone, water vapor, -carbon oxide, carbon dioxide, carbon suboxide, hydroxyl group (-OH),
Aldehyde group (-COH), acyl group (RCO-, -
Organic compounds having functional groups or bonds such as CRO), ketone groups (>Co), ether bonds (-〇-), ester bonds (-Coo-), and oxygen-containing heterocycles are used. Examples of organic compounds having a hydroxyl group include:
methanol, ethanol, propatool, butanol,
Allyl alcohol, fluoroethanol, fluorobutanol, phenol, cyclohexanol, benzyl alcohol, furfuryl alcohol, etc. are used. Examples of organic compounds having an aldehyde group include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, acrolein,
Benzaldehyde, furfural, etc. are used. Examples of organic compounds having an acyl group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, valmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, toluic acid, salicylic acid, and cinnamon. 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 furyl ether, ethyl vinyl ether, ethyl furyl ether,
Anisole, phenethole, phenyl ether, benzyl ether, phenylbenzyl ether, naphthyl ether, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydrobilane, dioxane, and the like 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, anthranilic acid Amyl, methyl phthalate, ethyl phthalate, butyl phthalate, etc. are used. Examples of heterocyclic compounds containing oxygen include furan, oxazole, furazane, biran, oxazine, morpholine, benzofuran, pandioxazole, chromene, chroman, dibenzofuran, xanthine, phenoxazine,
Oxolane, dioxolane, oxathiolane, oxadiazine, benzisoxazole, etc. are used.

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

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, and since there are few compounds in a gas phase, it is possible to vaporize through melting, evaporation, sublimation, etc. by heating or reduced pressure. As long as it can be obtained, either liquid phase or solid phase can be used. 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 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 increase the amount of alkali metal atoms added to the a-C film according to the present invention, and conversely, by decreasing the amount of alkali metal compound introduced, it is possible to increase the amount of alkali metal atoms added to the a-C film according to the present invention. , 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 the a-Si 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.

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 elemental atoms in the film is higher than 20,000 atomic ppm,
Phosphorus atoms or boron atoms, which, when added in small amounts, ensure suitable transport properties or polarity control effects, conversely exhibit the effect of lowering the resistance of the film, resulting in a decrease in charging ability. Therefore, the range of the amount of phosphorus atoms or boron atoms added in the present invention is important.

The amount of hydrogen atoms or fluorine atoms contained in the a-3T film of the present invention is necessarily determined from the manufacturing aspect of using glow discharge, but the total amount of silicon atoms and hydrogen atoms or silicon atoms and fluorine atoms On the other hand, the content is approximately 10 to 35 at%. Here, the content of hydrogen atoms or fluorine atoms in the film can be determined by using conventional methods of elemental analysis, such as ◯NH 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-3i film has a rich charge generation ability,
In general, in the laminated structure with the a-C film, which is the most characteristic feature of the present invention, generated carriers can be efficiently injected into the a-C film, contributing to suitable bright attenuation.

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

In the present invention, the amount of phosphorus atoms or boron atoms contained as a chemical modifier can be controlled mainly 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. If the amount of phosphine gas or diborane gas introduced is increased,
It is possible to increase the amount of phosphorus atoms or boron atoms added to the a-Si film according to the present invention, and conversely, if the amount of phosphine gas or diborane gas introduced is reduced, the a-5i film according to the present invention can be It is possible to reduce the amount of phosphorus atoms or boron atoms added into the film.

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

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

FIG. 3 shows, as another form, on a conductive substrate (1),
Charge transport layer (2), charge generation layer (3) and charge transport layer (2)
) 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). In Figure 2, electrons generated in the charge generation layer (3) travel towards the photoreceptor surface in charge transport N (2), and in Figure 3, electrons are generated in the charge generation layer (3). 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, charges are generated J!
The electrons generated in step (3) travel through the charge transport layer (2) on the front side towards the surface of the photoreceptor, forming an electrostatic latent image with a suitable brightness attenuation. On the other hand, when the surface of the photoreceptor is negatively charged and then used for image exposure, the behavior of electrons and holes can be exchanged to understand the mobility of carriers. In FIGS. 2 and 3, the irradiation light for image exposure passes through the charge transport layer, but since the charge transport layer according to the present invention has excellent translucency, it forms a suitable latent image. Is possible.

FIG. 4 shows a charge transport layer (2) on a conductive substrate (1) and charge generation! This figure shows a structure in which (3) and a surface protective layer (4) are sequentially laminated. In other words, it corresponds to the form in which a surface protective layer is provided in the form shown in Fig. 1, but in the form shown in Fig. 1, the outermost surface is a-3i with poor moisture resistance.
Since it is a film, in many cases it is preferable to provide a surface protective layer to ensure practical humidity stability. In the case of the configurations shown in FIGS. 2 and 3, since the outermost surface is a highly durable a-C film, 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 an intermediate layer (5), a charge generation layer (3), and a charge transport layer (2) on a conductive substrate (1) as a rough form.
This figure shows the structure formed by laminating the two layers together. 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-Si film, which ensures adhesiveness and injection blocking effect in most cases. It is preferable to provide an intermediate layer for this purpose. In the case of the configurations shown in FIGS. 1 and 3, since the bonding surface with the conductive substrate is the charge transport layer according to the present invention, which has excellent adhesiveness and injection blocking effect, it is not necessary to provide an intermediate layer. For example, an intermediate layer may be provided for the purpose of adjusting compatibility with a manufacturing process before forming a photosensitive layer, such as a pretreatment method for a conductive substrate.

FIG. 6 shows, as a further embodiment, an intermediate layer (5), a charge transport layer (2) and a charge generation layer (3) on a conductive substrate (1).
This figure shows a structure in which a surface protection layer (4) and a surface protection layer (4) are sequentially laminated. That is, it corresponds to the form shown in FIG. 1 with an intermediate layer and a surface protective layer provided.

The reason for providing the intermediate layer and the surface protective layer is the same as described above, and therefore, providing the intermediate layer and the surface protective layer in the configurations shown in FIGS. 2 and 3 can be an alternative form.

In the present invention, the intermediate layer and the surface protective layer are not particularly limited in terms of material or manufacturing method, and can be appropriately selected as long as a predetermined purpose can be achieved. 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 material be generated by a so-called plasma polymerization reaction, in which the material is introduced by force or the like and deposited as a solid phase by a recombination reaction on the substrate.

FIG. 7 shows a photoconductor manufacturing apparatus according to the present invention, and in the figure (701) to (706) are first to sixth tanks in which the raw material compound and carrier gas, which are in a gas phase at room temperature, are sealed, respectively. The tanks are the first to sixth control valves (707)
〜(712) and the first to sixth flow rate controllers (713)〜(
718). (719) to (721) in the figure
) are first to third containers filled with raw material compounds that are in a liquid or solid state at room temperature, and each container is heated by the first to third temperature controllers (722) to (724) for vaporization. Roughly speaking, each container has seventh to ninth control valves (725) to (727) and seventh to ninth flow rate regulators (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 is opened so that it 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).
) via a low frequency power supply (741L low pass filter (7
A DC power supply (743) is connected via 42),
A connection selection switch (744) determines whether power with different frequencies can be applied. 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 adjusted by a pressure control valve (745).
733) via the exhaust system selection valve (746), the diffusion pump (747L oil rotary pump (748), cooling exclusion device (749), mechanical booster pump (750), oil rotary pump (747), 748).For exhaust gas, use an appropriate exclusion device!(748).
After making it safe and harmless according to 53), it can be exhausted into the atmosphere.

For these exhaust system piping, pipe heaters (734
), it is said that heating is possible. For the same reason, the reaction chamber (733) can also be heated by a reaction chamber heater (751), and a conductive substrate (752) is placed on the electrode arranged inside.
will be installed. In FIG. 7, the conductive substrate (752) is fixedly arranged on the ground electrode (735), but it may also be fixedly arranged on the power application electrode (736), or even roughly arranged on both sides. good.

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-' to 10-' Torr, and the degree of vacuum is checked and the gas adsorbed inside the device is desorbed. At the same time, the electrode and the conductive substrate fixed to the electrode are heated using an electrode heater. The temperature is raised to a predetermined temperature.If necessary, an undercoat layer or a charge generation layer is provided in advance on the conductive substrate in order to obtain a desired photoreceptor structure from among the above-mentioned photoreceptor structures. The undercoat layer or charge generation layer may be installed using this device or a separate device.Next, the raw materials are collected from the first to sixth tanks and the first to third containers. Gas is introduced into the reaction chamber while being adjusted to a constant flow rate using the first to ninth flow rate controllers as appropriate, and a constant reduced pressure state is maintained in the reaction chamber using the pressure control valve.After the gas flow rate is stabilized, the connection selection switch is used to introduce the gas into the reaction chamber. For example, a high frequency iI source is selected and high frequency power is applied to the power application 'IX pole.A discharge is started between both electrodes, and over time a solid phase film is formed on the substrate.A-Si film or The a-C membrane is
It can be formed arbitrarily by changing the raw material gas. If the discharge is stopped once, the source gas composition is changed, and then the discharge is restarted again, films with different compositions can be stacked. 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.

Example 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 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 control 3iI devices under an output pressure of 1.0 Kg/cm2, respectively. (Flowed into tanks 713, 714, and 715.)

At the same time, potassium methacrylate (K-MA) gas is supplied from the second container (720) to the second temperature regulator (723) at a temperature of 270.
℃ into the eighth flow rate control u (729). Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 70 sec and the ethylene gas flow rate to 703 CCm.
The flow rate of % oxygen gas was set to 45 CCm, and the flow rate of potassium methacrylate gas was set to 8 sec, and the gas 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), vertical 5QX+j15
Using an aluminum substrate with a thickness of 0X and a thickness of 230 mm,
℃, 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 8 hours and 30 minutes under the following conditions, and a 315 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.

Organic elemental analysis of the a-CM obtained as described above revealed that 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, 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),
and the sixth control valve (712), and the first tank (70
Hydrogen gas from 1) and silane gas from the sixth tank (706) are supplied to the first and sixth tanks under an output pressure of IKg/cm2.
It was made to flow into the flow rate controllers (713 and 718). At the same time, the fourth control valve (710) is released and the fourth tank (710) is released.
Diborane gas diluted to 1100 pp with hydrogen gas from 04) was allowed to flow into the fourth flow rate controller (716) under an output pressure of 1.5 Kg/am2. Adjust the scale of each flow rate arc suppressor to set the flow rate of hydrogen gas to 200 sccm, the flow rate of silane gas to 101005e, and the flow rate of diborane gas diluted to 1100pp with hydrogen gas to 101005e, and let them flow into the reaction chamber (733). Ta. After each flow rate stabilized, the pressure inside the reaction chamber (733) reached 0.8 Torr.
The pressure regulating valve (745) was adjusted so that the temperature was r. On the other hand, the conductive substrate (752) on which the a-C film is formed is
After heating to 250℃ and with stable gas flow rate and pressure, a high frequency power source (739) is used to generate a frequency of 13.56M.
A power of 35 Watt was applied to the power application electrode (736) under Hz to generate glow discharge. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

When the obtained a-Si film was subjected to ONH analysis in metal (Itaba Seisakusho!! EMGA-1300), Auger analysis, and IMA analysis, it was found that the hydrogen atoms contained were 15 at % based on the total constituent atoms. , 100 atoms p of boron atoms
It cleared up at pm.

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 -730V (+480V), 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 48 .mu./.mu.m (31 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 17 seconds (approximately 12 seconds).
seconds), and from this it has sufficient charge retention performance b
Things were understood. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using white light.The amount of light required was 3.8 lux seconds (1.2 lux・seconds), and from this we can understand that it has sufficient photosensitivity performance.

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

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

Last trip, using the manufacturing apparatus according to the present invention, as shown in Fig. 1,
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

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

At the same time, lithium tertiary is supplied from the second container (720).
Butirad gas was allowed to flow into the eighth flow rate controller (729) at a second temperature controller (723) temperature of 170°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 sec, and the flow rate of lithium tert-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, as a conductive substrate (752), t! 150x width 50x thickness 3
Using an aluminum substrate of 1.5 mm in diameter, preheat it to 150°C, and with the gas flow rate and pressure stable, turn on the low frequency power supply (741) that was previously connected using the connection selection switch (744). 1 to the power application electrode (736)
A plasma polymerization reaction was performed for about 45 minutes by applying 50 Watts of power at a frequency of 600 KHz, 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.

When the a-C film obtained as described above was subjected to organic elemental analysis, the amount of hydrogen atoms contained was 53 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 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 were replaced, and the first control valve (7o7)
and the sixth control valve (712), and the first tank (70
Hydrogen gas from 1) and silane gas from the sixth tank (706) are supplied to the first and sixth tanks under an output pressure of IKg/Cm2.
It was made to flow into the flow rate controllers (713 and 718). At the same time, the fourth control valve (710) is released and the fourth tank (710) is released.
Diborane gas diluted to 1100 pp with hydrogen gas from 04) was flowed into the fourth flow rate controller (716) under an output pressure of 1.5 Kg/cm2. Adjust the scale of each flow controller to Fl to set the flow rate of hydrogen gas to 200SCCm, the flow rate of silane gas to 101005e, and the flow rate of hydrogen gas to 1100pp.
The flow rate of the diborane gas diluted to 10105e was set to 10105e, and the diborane gas was allowed to flow into the reaction chamber (733). After each flow rate stabilized, the pressure inside the reaction chamber (733) reached 0.8 Torr.
The pressure regulating valve (745) was adjusted so that the temperature was r. On the other hand, the conductive substrate (752) on which the a-C film is formed is
After heating to 250℃ and with stable gas flow rate and pressure, a high frequency power source (739) is used to generate a frequency of 13.56M.
A power of 35 Watt was applied to the power application electrode (736) under Hz to generate glow discharge. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-3i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), 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.
Met.

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 R high charging potential is -610V (+590V).In other words, since the total photoreceptor film thickness is 15°3μm, the charging ability per μm is It was extremely high at 40V/μm (38V/μm), and from this it was understood that it had sufficient charging performance.

In addition, the time required for the surface potential to decay from Vmax to 90% of Vmax in the dark was approximately 15 seconds (approximately 17
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential.The amount of light required was 1.6 lux·sec (1.5 lux・Seconds), and from this it was concluded that PE had sufficient photosensitivity performance.

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

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

Example 3 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. Valve (707,
708 and 709), and the first tank (701'
) from the second tank (702), acetylene gas from the second tank (702), and carbon dioxide gas from the third tank (703) under an output pressure of 1°0 Kg/am2, respectively, to the first, second, and third flow rate controllers. (713, 714, and 715). At the same time, lithium tert-butylade gas was flowed from the second container (720) into the eighth flow rate controller (729) at a second temperature controller (723) temperature of 220°C. Adjust the scale of each flow rate regulator to set the hydrogen gas flow rate to 200 seconds and the acetylene gas flow rate to 50 seconds.
ecm, the flow rate of carbon dioxide gas is 10s105e, and the flow rate of lithium tert-butylade gas is 18sec.
m, and flowed into the reaction chamber (733) from the main pipe (732) via an intermediate mixer (731). After each flow rate is stabilized, the pressure control valve (745) is opened so that the pressure in the reaction chamber (733) becomes 2.5 Torr.
adjusted. On the other hand, as the conductive substrate (752), w
Using an aluminum substrate of i50 x width 50 x thickness 3 mm, it was preheated to 220°C, and with the gas flow rate and pressure stable, it was connected to the high frequency power source (739) using the connection selection switch (744). ) and apply a power of 220 Watts to the power application electrode (736) at a frequency of 13.
．． A plasma polymerization reaction was performed for about 2 hours and 15 minutes by applying a frequency of 56 MHz, and a 15μ thick layer was formed on the conductive substrate (752).
A C film of m was formed as a charge transport layer. After the film formation is completed, the power application is stopped, the control valve is closed, and the reaction chamber (733
) was thoroughly evacuated.

Organic elemental analysis of the a-C film obtained as described above revealed that the amount of hydrogen atoms contained was 33 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 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), tetrafluorosilane gas is supplied from the second tank (702), and the sixth tank (702) is supplied with hydrogen gas.
06) was flowed into the first, second, and sixth flow controllers (713, 714, and 718) under an output pressure of IKg/cm2. At the same time, the fourth control valve (71
0) and 1 with hydrogen gas from the fourth tank (704).
Phosphine gas diluted to 100 pp is heated to an output pressure of 1.
It was made to flow into the fourth flow meter 81+ vessel (716) under 5 kg/am2. Adjust the scale of each flow rate regulator and set the flow rate of hydrogen gas to 200 sec, the flow rate of silane tetrafluoride gas to 70 sccm, the flow rate of silane gas to 50 sec, and the flow rate of phosphine gas diluted to 100 ppm with hydrogen gas to 10105e. , into the reaction chamber (733).

After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 0.8 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 240°C, and is heated to 13.56 MH2 from a high frequency power source (739) under a stable gas flow rate and pressure. Apply 40 Watts of power to the power application electrode (736) to prevent glow discharge from occurring. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-5i film was subjected to ONH analysis in metal (Itaba Seisakusho*EMGA-1300), Auger analysis, and IM.
Analysis A revealed that the hydrogen atoms contained were 26 at %, the phosphorus atoms were 15 at ppm, and the fluorine atoms were 5.6 at % based on the total constituent atoms.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -550V (+780V), that is,
Since the total photoreceptor film thickness was 15.3 .mu.m, the charging ability per 1 .mu.m was extremely high at 36 .mu./.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 11 seconds (approximately 17 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, bright decay was performed using white light to a surface potential of 20% of the highest charging potential.・seconds), and from this it was understood that it had sufficient photosensitivity performance.

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

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

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. Valve (707,
708 and 709), and the first tank (701)
Hydrogen gas from the second tank (702), butadiene gas from the third tank (703), and oxygen gas from the third tank (703) were 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 260.
℃ into the eighth flow rate controller (729).

Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 120 sccm and the butadiene gas flow rate to 50 seconds.
, set the flow rate of oxygen gas to esccm, and the flow rate of potassium methacrylate gas to 5 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 inside the reaction chamber (733) was 2.2 Torr. On the other hand, as the conductive substrate (752),! 50 x paddle 50 x 53m
Using an aluminum substrate of M, preheat it 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), 17 to the power application electrode (736)
A plasma polymerization reaction was carried out for about 1 hour and 30 minutes by applying a power of 0 Watt at a frequency of 800 KHz 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 of the a-CI'A obtained as described above revealed that the amount of hydrogen atoms contained was 41 atomic % based on the total amount of carbon atoms and hydrogen atoms. Furthermore, according to Auger analysis, the amount of alkali metal atoms contained, that is, potassium atoms, is 0.9 at% based on the total constituent atoms.
Met. 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 were replaced, and the first control valve (7o7)
and the sixth control valve (712), and the first tank (70
Hydrogen gas from 1) and silane gas from the sixth tank (706) are supplied to the first and sixth tanks under an output pressure of IKg/cm2.
It was made to flow into the flow rate controllers (713 and 718). At the same time, the fourth control valve (710) is released and the fourth tank (710) is released.
Phosphine gas diluted to 1100 pp with hydrogen gas from 04) was flowed into the fourth flow rate controller (716) under an output pressure of 1.5 Kg/cm2. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200sCCm.1 Silane gas flow rate to 101005e, hydrogen gas to 1100p.
The flow rate of phosphine gas diluted to p is 101005e
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 (752) on which an a-C film is formed
is heated to 200℃, and when the gas flow rate and pressure are stable, the frequency is 13.5 from the high frequency power supply (739).
55Watt 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-3i 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 atomic % and the phosphorus atoms were 115 atomic ppm based on the total constituent atoms.
Met.

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 -550V (+960V), that is,
All photoconductor I! Since the J thickness is 15°3μm, it is 1μm.
The charging capacity per charge was extremely high at 36V/μm (63V/μm), and from this it was understood that the charging performance was sufficient.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 19 seconds (approximately 36 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, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential.The amount of light required was 2.1 lux·sec (8.4 lux・seconds), and from this it was understood that it had sufficient photosensitivity performance.

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

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

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. 709
)! hydrogen gas from the first tank (701) and oxygen gas from the third tank (703) at an output pressure of 1.0.
The first and third flow controllers (713
, and 715). At the same time, the first container (7
19) from the styrene gas to the first temperature controller (722) at a temperature of 4.
into the seventh flow controller (728) at 0°C, and
Second edition! (720), lithium tertiary-butylade gas was flowed into the eighth flow rate controller (729) at a second temperature control M (723) temperature of 170°C. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 70se.
cm, the flow rate of styrene gas was set to 40 sec, the flow rate of oxygen gas was set to 10105e, and the flow rate of lithium tert-butylade gas was set to 8 sec, and the reaction was carried out from the main pipe (732) via an intermediate mixer (731). It flowed into the room (733). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 2°2 Torr. On the other hand, the conductive substrate (752) is 50 x 5 Q x 3 mm thick.
Using an aluminum substrate, heat it in advance to 90°C, and with the gas flow rate and pressure stable, connect it to the low frequency power supply (744) using the connection selection switch (744).
741) and apply 150W to the power application electrode (736).
Att power is applied at a frequency of 120KHz and approximately 4
A plasma polymerization reaction was performed for 5 minutes, and a 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-Cp4 obtained as described above revealed that the amount of hydrogen atoms contained was 47 at % based on the total amount of carbon atoms and hydrogen atoms. Furthermore, according to Auger analysis, the amount of alkali metal atoms contained, that is, lithium atoms, is 1.7 at% based on the total constituent atoms.
Met. 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 FI control valve (708) and the sixth control valve (712) are released, hydrogen gas is supplied from the first tank (701), tetrafluorosilane gas is supplied from the second tank (702), and the sixth tank (
706) to the first, second, and sixth flow rate controllers (713, 714,
and 718). At the same time, the fourth control valve (7
10), and diborane gas diluted to 1100 pp with hydrogen gas from the fourth tank (704) was brought to an output pressure of 1.
into the fourth flow restrictor (716) under 5Kg/am2;
I let it flow in. Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 200S CCm%, the flow rate of silane tetrafluoride gas to 50 sccm, the flow rate of silane gas to 50 seconds, and the flow rate of diborane gas diluted to 1100 pp with hydrogen gas to 101005e, It was made to flow into the reaction chamber (733). After each flow rate is stabilized, the pressure regulating valve (74) is adjusted so that the pressure in the reaction chamber (733) becomes 0.8 Torr.
5) was adjusted. 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. Power application electrode (736
) was applied with a power of 35 Watts to generate glow discharge. This discharge was carried out for 5 minutes to obtain a charge generation layer with a Jg diameter 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 21 at% of the total constituent atoms, and the boron atoms were 100 at pI.
)rrh fluorine atoms were 5 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 -680V (+540V), that is,
Since the total photoreceptor film thickness was 15.3 .mu.m, the charging ability per 1 .mu.m was extremely high at 44 .mu.m/.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 11 seconds (approximately 10 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 4.3 lux·sec (1.5 lux・seconds), and from this it was understood that it had sufficient photosensitivity performance.

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

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

In the last example, the manufacturing apparatus according to the present invention was constructed 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: A charge transport layer of a photoreceptor according to the present invention was formed in the same manner as in Example 2.

Charge generation layer forming step: Next, some of the tanks are replaced, and 1st: A joint (707)
, the second control valve (708), and the sixth control valve (712) are released, hydrogen gas is supplied from the first tank (701), tetrafluorosilane gas is supplied from the second tank (702), and the sixth tank (
706) to the first, second, and sixth flow rate controllers (713, 714,
and 718). At the same time, the fourth control valve (7
10), and diborane gas diluted to 1100 pp with hydrogen gas from the fourth tank (704) was brought to an output pressure of 1.
into the fourth flow controller (716) under 5Kg/cm2;
Don't let it flow in. Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 200 s, the flow rate of c cms tetrafluorosilane gas to 50 sec, the flow rate of silane gas to 50 sec,
The flow rate of diborane gas diluted to 1100 pp with hydrogen gas is set to 10105e, and is not allowed to flow into the reaction chamber (733). After each flow rate is stabilized, the reaction chamber (733)
Pressure regulating valve (7) so that the internal pressure is 0.8 Torr.
45) was adjusted. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 230°C, and the high-frequency power source (739) is heated to stabilize the gas flow rate and pressure.
The power application electrode (73
6), a power of 35 Watts was applied to generate glow discharge. This discharge was performed for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-St 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 atomic % and the boron atoms were 13 atomic ppm based on the total constituent atoms.
% fluorine atoms was 5 at.

Characteristics: When the obtained photoreceptor was used in a conventional Carlson process under negative charging and positive WIN, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -670V (+690V).In other words, since the total photoreceptor film thickness is 15°3μm, the charging ability per 1μm is 44V. The charging performance was extremely high at 1/μm (45V/μm), and it was understood from this that it had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 13 seconds (approximately 14 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 amount of light required was 1.8 lux·sec (1, flux·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.

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: A charge transport layer of a photoreceptor according to the present invention was formed in the same manner as in Example 1.

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), tetrafluorosilane gas is supplied from the second tank (702), and the sixth tank (702) is supplied with hydrogen gas.
06) into the first, second, and sixth flow rate controls M (713, 714, and 718) under an output pressure of IKg/cm2. At the same time, the fourth control valve (71
0) and 1 with hydrogen gas from the fourth tank (704).
Phosphine gas diluted to 100 pp is heated to an output pressure of 1.
into the fourth flow controller (716) under 5Kg/am2;
I let it flow in. Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 250 sec and the flow rate of silane tetrafluoride gas to 50 sec.
sccm, the flow rate of silane gas is 50 seconds, and the flow rate of phosphine gas diluted to 1100 pp with hydrogen gas is 1.
It was set at 1005 ca and flowed into the reaction chamber (733).

After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 1.0 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 230°C, and is heated to 13.56 MH2 from a high frequency power source (739) under a stable gas flow rate and pressure. A power of 40 Watts was applied to the power application electrode (736) to generate glow discharge. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-Si film was then 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 22 at.% of the total constituent atoms, and the phosphorus atoms were 108 at.ppm.
, the fluorine atoms were 5 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 (+840V), 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 .mu.m/.mu.m (55 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 a surface potential of 90% of Vmax in the dark was approximately 8 seconds (approximately 18 seconds), which clearly indicates that it has sufficient charge retention performance. Ta. In addition, after initial electrification to the highest charging potential,
The amount of light required to brightly attenuate the surface potential to 20% of the highest charging potential using white light was 1.4 lux·sec (5°4 lux·sec), which indicates that there is sufficient It was understood that it has photosensitivity performance.

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

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

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

Charge transport layer forming step: A charge transport layer of a photoreceptor according to the present invention was formed in the same manner as in Example 8.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
and the sixth control valve (712), and the first tank (70
Hydrogen gas from 1) and silane gas from the sixth tank (706) are supplied to the first and sixth tanks under an output pressure of IKg/Cm2.
The liquid was allowed to flow into the flow rate controllers (713 and 718). At the same time, the fourth control valve (710) is released and the fourth tank (710) is released.
The phosphine gas diluted to 1100 pp with hydrogen gas from 04) was flowed into the fourth flow restrictor (716) under an output pressure of 1.5 Kg/cm2. Adjust the scale of each flow rate regulator to set the hydrogen gas flow rate to 2005 cam and the silane gas flow rate to LOOsccm hydrogen gas to 100 p p
The flow rate of the phosphine gas diluted to 10105e was set to 10105e, and the flow rate was made to flow into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 0.8T.
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 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 carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-3t film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
MA analysis revealed that the hydrogen atoms contained were 18 atomic % and the phosphorus atoms contained were 12 atomic ppm based on the total constituent atoms.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values at the time of positive charging are shown in parentheses, and the highest charging potential grows at -490V (+720V), that is,
Since the total photoreceptor film thickness was 15°3 μm, the charging capacity per μm was extremely high at 32 V/μm (47 V/μm), and from this it was understood that it had sufficient W charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 12 seconds (approximately 18
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using white light.The amount of light required was 1.2 lux seconds (2, flux seconds), and from this it was understood that it had sufficient photosensitivity performance.

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

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

[Brief explanation of the drawing]

1 to 6 are drawings showing the structure of a photoreceptor according to the present invention, and FIGS. 7 to 8 are drawings showing an apparatus for manufacturing a photoreceptor according to the invention. Applicant: Minolta Camera Co., Ltd. Figure 1 Figure 3 Figure 5 Figure 2 Figure 4 Figure 6 Procedural Amendment October 21, 1988

Claims (1)

[Claims] In a functionally separated photoreceptor having a charge generation layer and a charge transport layer, the charge transport layer is a hydrogenated amorphous carbon film containing at least oxygen atoms and alkali metal atoms; A photoreceptor characterized in that it is a hydrogenated amorphous silicon film containing at least one of phosphorus atoms and boron atoms, or a fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms.