JPS6382448A - Photosensitive body - Google Patents

Abstract

PURPOSE:To improve the transferability of an electric charge transfer layer by providing the charge transfer layer consisting of hydrogenated amorphous carbon contg. Si or/and Ge and an electric charge generating layer contg. specific atoms together with oxygen atoms. CONSTITUTION:For example, the charge transfer layer 2 and the charge generat ing layer 3 are successively laminated on a conductive substrate 1. The layer 2 consists of the hydrogenated amorphous carbon film contg. Si or/and Ge. The layer 3 consists of the hydrogenated or fluorinated amorphous silicon film contg. O and contg. P or/and B. Both the layers 2 and 3 are preferably formed by glow discharge. The charge transfer layer having the adequate transferability and excellent electric chargeability, durability, etc., is thereby obtd. The reduc tion in the film thickness of the charge generating layer is permitted as well.

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

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

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

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

By the way, the amorphous carbon film itself has been known for a long time as a plasma organic polymerized film, for example, diene (M
, 5hen) and Bell (A, T.

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

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

However, plasma organic polymer films prepared by conventional methods are used only for applications that 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 high resistance plasma polymerized film of 1013 to 1015 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. 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-5i
However, it does not solve the above-mentioned essential problems.

For example, JP-A-50-20728 discloses that a polymer film formed by glow discharge polymerization is applied as a protective layer on the surface of a polyvinylcarbazole-selenium photoreceptor in an amount of 0.1 to 1 ll.
A photoreceptor with a length of 1 m is disclosed. Japanese Unexamined Patent Publication 1986-21
Japanese Patent No. 4859 discloses a technique of plasma polymerizing an organic hydrocarbon monomer such as styrene or acetylene as a protective layer on the surface of an amorphous silicon photoreceptor to form a film of about 5 μm. Japanese Patent Publication No. 60-61761
The publication discloses a photosensitive member 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 thickness M 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 regarding charge transport properties, and they do not solve the above-mentioned essential interlayer that a-Si has. do not have.

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

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

Philosophical Magazine (Philosophical Magazine) published in 1976 by
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 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 have been 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.

Problem to be solved by Φ As mentioned above, plasma organic polymer films conventionally used in electrophotographic photoreceptors have been used only as so-called undercoat layers or overcoat layers; It is a film that does not require any function, and is used based on the judgment that the organic polymer film is insulating. Therefore, it can only be used as an extremely thin film with a thickness of about 5 μm at most, and carriers either pass through the film by tunneling effect, or if a tunneling effect cannot be expected, there is virtually no problem with the generation of residual potential. It is only used in thin films that are only small enough to last. Furthermore, amorphous silicon films conventionally used in electrophotography are so-called thick films, which have many disadvantages in terms of cost, productivity, and the like.

While considering the application of an amorphous carbon film to an electrophotographic photoreceptor, the present inventors discovered that a hydrogenated amorphous carbon film, which was originally thought to be insulating, was found to contain at least one of silicon atoms and germanium atoms. By containing , it has charge transport properties and is easily suitable for stacking with a hydrogenated or fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms and also containing oxygen atoms. It was discovered that the electrophotographic properties began to show certain electrophotographic properties. There are many points in the theoretical interpretation that are unclear even to the inventor, so it is not possible to discuss the details in detail.
A band formed by electrons in a relatively unstable energy state, such as π electrons, unpaired electrons, and residual free radicals, captured in a hydrogenated amorphous carbon film containing at least one of silicon atoms and germanium atoms. An energy level whose structure is similar in conduction band or valence band to the band structure formed by a hydrogenated or fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms and oxygen atoms. Therefore, carriers generated in a hydrogenated or fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms and oxygen atoms can easily form at least one of silicon atoms and germanium atoms. The carriers are injected into the hydrogenated amorphous carbon film containing at least one of silicon atoms and germanium atoms due to the action of the electrons in the relatively unstable energy state described above. It is presumed that this is because it can run suitably through the carbon film.

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

Means for solving the problem, 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 silicon atoms and germanium atoms generated from a plasma polymerization reaction. A hydrogenated amorphous carbon film containing at least one of phosphorus atoms and boron atoms, and a hydrogenated or fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms and oxygen atoms. Regarding a photoreceptor characterized in that it is a film (hereinafter, the charge transport layer according to the present invention is referred to as a-C film and the charge generation layer is referred to as a-
5i 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 one of silicon atoms and germanium atoms produced by glow discharge as a charge transport layer, and a hydrogenated amorphous carbon film containing at least one of silicon atoms and germanium 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 and oxygen atoms. Although the charge transport layer does not have clear photoconductivity for visible light or light with a wavelength near semiconductor laser light, it has suitable transport properties, and has good charging ability, durability, and weather resistance. It has excellent electrophotographic photoreceptor performance such as durability and environmental pollution resistance, and is also excellent in light transmission, so it provides an extremely high degree of freedom when forming a laminated structure as a function-separated photoreceptor. . In addition, the charge generation layer has excellent photoconductivity for visible light or light with a wavelength near semiconductor laser light, and has an extremely thin film thickness compared to conventional amorphous silicon photoreceptors. 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, tritecane, tetradecane, bentatecane, hexacosane, hebutatecane, octadecane, nonadecane, eicosane, heneicosane, tocosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, Normal paraffins such as nonacosane, triacontane, todoriacontane, pentatriacontane, 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.
Isoparaffins such as 2.4-trimethylpentane, 2,3°3-trimethylpentane, 2.3.4-)dimethylpentane, 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-2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-
Olefins such as nonene, 1-decene, diolefins such as allene, methylalene, butadiene, pentadiene, hexadiene, cyclopentadiene, and triolefins such as ocimene, alloocimene, myrcene, hexatriene, and Acetylene, butadiyne, 1゜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, tervirune, phelandrene, sylvestrene, thuene, carene, pinene, bornylene, camphene, and phene. Terpenes such as chen, cycloundecane, tricyclene, bisabolene, zingiberene, curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, camphorene, phylloclatene, bodocarbrene, mirene, and steroids are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, pseudocumene, mesitylene, prenitene, isodurene, durene,
Pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, biphenyl, terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

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

The amount of hydrogen atoms contained in a-CfJ in the present invention is inevitably determined by the production process using glow discharge, but it is approximately 30% 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, O
This can be determined by using NH 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 μm; if it is thinner than 5 μm, the charging potential will be low, making it impossible to obtain a sufficient density of the copied image. Moreover, if it is thicker than 50 μm, it is not preferable in terms of productivity.

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

In the process of forming an a-C film from a raw material gas in the present invention, the raw material gas is formed through a plasma state generated by a plasma method using direct current, low frequency, cavity frequency, microwave, etc. Although this method is the most preferable, it may also be formed through an ion state generated by an ionization vapor deposition method, an ion beam vapor deposition method, etc., or an intermediate state generated by a vacuum vapor deposition method, a sputtering method, etc. It may be formed from sexual particles, or it may be formed from a combination of these particles.

In the present invention, in addition to hydrocarbons, a silicon compound or a germanium compound is used as a raw material for adding at least silicon atoms or germanium atoms into the a-C film. The phase state of the silicon compound or germanium compound does not necessarily have to be a gas phase at room temperature and normal pressure, but it can be 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 can also be used in phases. Examples of the silicon compound or metal germanide include silane, disilane, fluorinated silane,
Inorganic compounds such as germane and organic compounds such as metal phthalocyanine and metal alcoholade are used.

In the present invention, the amount of silicon atoms (or germanium atoms) contained as a chemical modifier is 10 at% or less based on the total constituent atoms.Here, the content of silicon atoms or germanium atoms in the film is This can be determined by conventional methods of elemental analysis, such as Auger analysis.If silicon atoms or germanium atoms are not included, suitable transport properties cannot be ensured, and deterioration over time after film formation is likely to occur. On the other hand, when the amount of silicon atoms exceeds 10 at %, the silicon atoms, which had guaranteed good transport properties when added in small amounts, instead work to increase the resistance of the film, resulting in a decrease in sensitivity. On the other hand, if the amount of germanium atoms is 1
If the amount exceeds 0 atomic %, the germanium atoms, which had ensured suitable transport properties when added in small amounts, instead exhibit the effect of lowering the resistance of the film, resulting in a decrease in charging ability. Therefore,
In the present invention, the range of the amount of silicon atoms or germanium atoms added is important.

In the present invention, the amount of silicon atoms or germanium atoms contained as a chemical modifier is mainly controlled by increasing or decreasing the amount of the silicon compound or germanium compound introduced into the reaction chamber in which the plasma reaction is performed. Is possible. By increasing the amount of silicon compound or germanium compound introduced, it is possible to reduce the amount of silicon atoms or germanium atoms added to a-Cp according to the present invention. By reducing the amount of compound introduced, a-
It is possible to reduce the amount of silicon atoms or germanium atoms added to the C film.

In the present invention, silane gas, disilane gas, or fluorinated silane gas is used to form the a-Si film. Furthermore, phosphine gas, diborane gas, or the like is used as a raw material gas for incorporating phosphorus atoms or boron atoms as chemical modifiers into the film. Furthermore, an oxygen compound gas such as oxygen gas, nitrous oxide gas, ozone gas, or -carbon oxide gas is used as a raw material gas for containing oxygen atoms as a chemical modifier in 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 boron 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.

In the present invention, the amount of oxygen atoms contained as a chemical modifier is 0.001 to 1 atomic% based on the total constituent atoms.
It is. Here, the content of oxygen atoms in the film can be determined by a conventional method of elemental analysis, such as Auger analysis or IMA analysis. When the content of oxygen atoms in the film is lower than o or ooi atomic percent, the electric resistance value of the a-5i film becomes low, making it difficult for the a-Si film to be subjected to an electric field due to corona charging, etc., and photoexcited carriers are It is not necessarily efficient to inject into the aC film, resulting in a decrease in sensitivity. Furthermore, the charging ability is also reduced. If the content of oxygen atoms in the film is higher than 1 atomic %, the electrical resistance of the a-Si film becomes too high, resulting in a decrease in the generation efficiency and mobile speed of photoexcited carriers, and a decrease in sensitivity. invite. Therefore, the range of the amount of oxygen atoms added in the present invention is important.

The amount of hydrogen atoms or fluorine atoms contained in the a-3i 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 the Miya method 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-3i film has a rich charge generation ability,
Furthermore, the most characteristic feature of the present invention is a CFJ
In the laminated structure with the a-C film, 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 oxygen atoms, phosphorus atoms, or boron atoms contained as chemical modifiers is mainly determined by the amount of oxygen compound gas, phosphine gas, or diborane gas introduced into the reaction chamber in which the plasma reaction is performed. This can be controlled by increasing or decreasing the amount of introduced. By increasing the amount of oxygen compound gas, phosphine gas, or diborane gas introduced, oxygen atoms, phosphorus atoms,
Alternatively, it is possible to increase the amount of boron atoms added,
Conversely, if the amount of oxygen compound gas, phosphine gas, or diborane gas introduced is reduced, the amount of oxygen atoms, phosphorus atoms, or boron atoms added to the a-3i film according to the present invention can be reduced. is possible.

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

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

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

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

FIG. 5 shows an intermediate layer (5), a charge generation layer (3), and a charge transport N (2) on a conductive substrate (1) as a rough form.
This figure shows a structure in which these are sequentially laminated. That is, the second
This corresponds to the form shown in the figure with an intermediate layer provided, but in the form shown in Fig. 2, the bonding surface with the conductive substrate is a-3iFi, so in most cases adhesiveness and injection blocking effect are ensured. Therefore, it is preferable to provide an intermediate layer. In the case of the configurations shown in FIGS. 1 and 3, there is no need to provide an intermediate layer because 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. 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 rough form, 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 N(4) and a surface protection layer N(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-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 the gas phase by discharge under reduced pressure, and diffuses active neutral species or charged i species contained in the generated plasma atmosphere onto the substrate, using electric force or It is preferable that the material be generated by a so-called plasma polymerization reaction, which is induced by magnetic 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 regulators (713)~(
718). (719) to (721) in the figure
) are the first to third containers containing raw material compounds that are in the i-phase or solid phase state at room temperature, and each container is heated by the first to third temperature N units (722) to (724) for vaporization. Each container has seventh to ninth control valves (725) to (727) and seventh to ninth flow fn TI.
It is connected to J Goki (728) to (730). After these gases are mixed in a mixer (731), they are passed through the main pipe (731).
32) into the reaction chamber (733). The pipes in the middle are designed to prevent the vaporized gas from the raw material compound, which is in a liquid or solid state at room temperature, from condensing on the way.
Heat can be supplied by a P8 device (734) in front of the piping, which is appropriately placed. A ground electrode (735) and a 7IIlr electrode (736) are installed facing each other in the reaction chamber, and each electrode can be heated by an electrode heater (737). A high frequency power source (739) is connected to the power application electrode (736) via a high frequency power matching box (738), and a low frequency power matching device is connected to the power applying electrode (736). (740) to the low frequency power supply (74
1), DC power supply (
743) is connected, and the connection selection switch (744
), it is possible to apply power with different frequencies.

The pressure in the reaction chamber (733) can be adjusted by a pressure control valve (745), and the pressure in the reaction chamber (733) can be reduced by a diffusion pump (747) via an exhaust system selection valve (746).
, oil rotary pump (748), or cooling exclusion device (748)
49), mechanical booster pump (750),
This is done by an oil rotary pump (748). The exhaust gas is made safe and harmless by a suitable exclusion device (753) and then exhausted into the atmosphere. These exhaust system pipings are also designed to prevent the vaporized gas from the raw material compounds, which are in a liquid or solid state at room temperature, from condensing on the way.
Heat can be supplied by appropriately placed pipe heaters (734). For the same reason, the reaction chamber (733) can also be heated by a reaction chamber heater (751), and a conductive substrate (752) is installed on the electrode arranged inside. 7th
In the figure, the conductive substrate (752) is the ground electrode (735)
Although it is fixedly arranged on the power application electrode (736), it may be fixedly arranged on the power application electrode (736), or may be arranged roughly on both sides.

FIG. 8 shows another embodiment of the photoconductor manufacturing apparatus according to the present invention, which is similar to the photoconductor manufacturing apparatus according to the present invention shown in FIG. 7 except for the internal configuration of the reaction chamber (833). can be,
The appended numbers can be understood by replacing the 700s with 800s. In FIG. 8, the reaction chamber (83
3) A cylindrical conductive substrate (852) that also serves as the ground electrode (735) in FIG. 7 is installed inside, and an electrode heater (837) is placed inside. Conductive substrate (
852) There is also a cylindrical power application electrode (
836) is arranged, and an electrode heater (837) is arranged 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-Si film or the a-C film can be formed arbitrarily by changing the source gas. Films with different compositions can be laminated by once stopping the discharge, changing the source gas composition, and then restarting the discharge. It is also possible to gradually change only the raw material gas flow rate while sustaining the discharge, and to stack films of different compositions with a gradient.

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

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

X Travel Ken 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. 4 control valve (710) is released, hydrogen gas is supplied from the first tank (701), and germane gas is supplied from the fourth tank (704) to the first and fourth flow rate controls under an output pressure of 1.0 kg/cm2. It was made to flow into the kaiki (713 and 716). at the same time,
Myrcene gas is supplied from the first container (719) to the first temperature controller (7
22) It was made to flow into the seventh flow rate control unit (728) at a temperature of 70°C. Using each flow rate controller, set the flow rate of hydrogen gas to 20 sec, the flow rate of germane gas to 5 sec, and the flow rate of myrcene gas to 5 sec. The liquid then flowed into the reaction chamber (733). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 1.5 Torr. On the other hand, the conductive substrate (752) is 50m x 50m x 3m thick.
Using an aluminum substrate of M, 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 with the connection selection switch (744), 1 for 11 power application poles (736)
A plasma polymerization reaction was carried out for about 3 hours and 40 minutes by applying a power of 10 Watts at a frequency of 500 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.

When organic elemental analysis was performed on the a-C film obtained as described above, the amount of hydrogen atoms contained was 45 at % based on the total amount of carbon atoms and hydrogen atoms. Further, according to Auger analysis, the amount of germanium atoms that could be contained was 2.8 at % based on the total constituent atoms.

Charge generation layer forming step: Next, the first control valve (707) and the fifth control valve (711)
, and the sixth control valve (712), and the first tank (7
01), nitrous oxide gas from the fifth tank (705), and silane gas from the sixth tank (706) at the first, fifth, and sixth tanks under an output pressure of I Kg/Cm2.
It was made to flow into the flow controllers (713, 717, and 718). At the same time, the fourth control valve (710) is opened, and diborane gas diluted to 1100 pp with hydrogen gas is supplied from the fourth tank (704) into the fourth flow rate controller (716) under an output pressure of 1.5 kg/cm2. I let it flow.

Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200.
secm, the flow rate of nitrous oxide gas to 0.01 sccrr
+, silane gas flow rate 101005e.

The flow rate of diborane gas diluted to 1100pI with hydrogen gas was set to 10105e, and
3) It was allowed to flow into the interior. After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 0.8 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 250°C, and is heated at a frequency of 13.56 MHz from a high frequency power source (739) while the gas flow rate and pressure are stable. A power of 35 Watts was applied to the power application electrode (736) to generate glow discharge. This discharge was carried out for 5 minutes, and a thick 0
．． A charge generation layer of 3 μm was obtained.

The obtained a-3i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by iba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 22 atomic% and the boron atoms were 10 atomic ppm based on the total constituent atoms.
, oxygen atoms were 0.001 atomic %.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -490V (+480■), 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 (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 21 seconds (approximately 23 seconds).
seconds), and from this we can understand that it has sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using white light. seconds), and from this it was understood that it had sufficient photosensitivity performance.

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

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

Example 2 Using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Control valve (7
08) and the sixth control valve (712) are released, hydrogen gas is supplied from the first tank (701), ethylene gas is supplied from the second tank (702), and silane gas is supplied from the sixth tank (706) at an output pressure of 1. ．． ○The first, second, and sixth flow controllers (713, 714, and 718 under Kg/am2)
). Using each flow rate controller, set the flow rate of hydrogen gas to 60 sec and the flow rate of ethylene gas to 60 SCC.
m, and the flow rate of silane gas is set to 3 seconds, and the main pipe (732
) into the reaction chamber (733). After each flow rate stabilized, the pressure inside the reaction chamber (733) reached 1.8 Torr.
The pressure regulating valve (745) was adjusted so that the temperature was r. On the other hand, as the conductive substrate (752), use an aluminum substrate of 50 x 50 x 3 mm thick, heat it to 250°C in advance, and when the gas flow rate and pressure are stable, connect the connection selection switch (744) in advance. Turn on the high frequency power supply (739) connected to
A plasma polymerization reaction was carried out for about 10 hours by applying a power of 180 Watts at a frequency of 13.56 MHz 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-σ film obtained as described above revealed that the amount of hydrogen atoms contained was 45 at % based on the total amount of carbon atoms and hydrogen atoms. Also,
According to Auger analysis, the amount of silicon atoms contained was 0.4 at % based on the total constituent atoms.

Charge generation layer forming step: Next, the first control valve (707) and the fifth control valve (711
), and the sixth control valve (712) are released, and the first tank (
Hydrogen gas from the fifth tank (701), oxygen gas from the fifth tank (705), and silane gas from the sixth tank (706) are supplied to the first, fifth, and sixth flow restrictors (713) under an output pressure of IKg/cm2. , 717, and 718).

At the same time, the fourth control valve (710) is released and the fourth tank (
Diborane gas diluted to 1100 pp with hydrogen gas (704) was allowed to flow into the fourth flow restrictor (716) under an output pressure L of 5 kg/cm2. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec, the oxygen gas flow rate to 0.5 sec, and the silane gas flow rate to 101 sec.
005e, the flow rate of diborane gas diluted to 1100pp with hydrogen gas was set to 10105e, and 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 0.9 Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed has been heated to 230°C, and with the gas flow rate and pressure stabilized, it is heated at a frequency of 13.56 MHz from a high frequency power source (739). A power of 35 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-3iJ15j was subjected to ONH analysis in metal (
Itaba fabrication fracture EMGA-1300), Auger analysis,
When IMA analysis was carried out, the hydrogen atoms contained were 2Q atomic %, the boron atoms were 12 atomic ppm, and the oxygen atoms were 0.1 atomic %, 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 -650V (+680V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 42 V/.mu.m (44 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to a surface potential of 9% of Vmax in the dark was approximately 17 seconds (approximately 16
seconds), and from this it was understood that it had sufficient charge retention performance. Furthermore, 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, and the amount of light required was 1. flux-second (1,'4 lux-second), and from this it was understood that it had sufficient photosensitivity performance.

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

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

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

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Control valve (70
8) and the sixth regulating valve (712) are released, hydrogen gas is supplied from the first tank (701), butadiene gas is supplied from the second tank (702), and silane gas is supplied from the sixth tank (706) at an output pressure of 1, respectively. The 1st, 2nd, and 6th flow rate control domains (713, 714, and 718
). Using each flow rate controller, set the flow rate of hydrogen gas to 60 sec, and the flow rate of butadiene gas to 60 sec.
Cm% and the flow rate of silane gas were set to 5 sec, and the main pipe (73
2) into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) increases to 1.8To
The pressure regulating valve (745) was adjusted so that rr. On the other hand, as a conductive substrate (752), fir 50× horizontal 50×
Using a 3 mm thick aluminum substrate, preheat it to 250°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). , power application electrode (736)
A power of 120 Watts was applied at a frequency of 400 KHz to carry out a plasma polymerization reaction for about 40 minutes, thereby forming an a-C film with a thickness of 15 μm 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 53 at % based on the total amount of carbon atoms and hydrogen atoms. Moreover, the amount of silane atoms contained was 5.2 at % based on the total constituent atoms according to Auger analysis.

Charge generation layer forming step: Next, the first control valve (707) and the third control valve (709)
, the fifth control valve (711), and the sixth control valve (712) are released, hydrogen gas is supplied from the first tank (701), tetrafluorosilane gas is supplied from the third tank (703), and the fifth tank (70
5) and silane gas from the sixth tank (706) through the first, third, fifth, and sixth flow rate controllers (713, 715, 71) under an output pressure of IKg/cm2.
7, and 718). At the same time, the fourth control valve (710) is opened, and diborane gas diluted to 1-00 ppm with hydrogen gas is supplied from the fourth tank (704) under the fourth flow rate control under an output pressure of 1.5 Kg/cm2. Vessel (7
16) Inflow began to flow inside. The scale of each flow rate controller was adjusted to set the flow rate of hydrogen gas to 200 sCCm and the flow rate of silane tetrafluoride gas to 50 sccm.

The flow rate of nitrous oxide gas was set to lsecms, the flow rate of silane gas was set to 50 sccm, and the flow rate of diborane gas diluted to 1100 pp with hydrogen gas was set to 10105e, and the mixture was allowed to flow into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 0.9 Torr.
The pressure control valve (745) was adjusted so that on the other hand,
The conductive substrate (752) on which the a-C film is formed is 2
After heating to 50℃ and with stable gas flow rate and pressure, a high frequency power supply (739) is used to generate a frequency of 13℃ and 66MH.
z, a power of 35 Watt 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-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 22 at % of the total constituent atoms, and the boron atoms were 10 at pPm.
The N fluorine atoms were S atom %, and the oxygen atoms were 0.1 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 at the time of positive charging are shown in parentheses, and the highest charging potential is -860V (+830V), that is,
Since the total photoreceptor film thickness was 15.3 .mu.m, the charging ability per 1 .mu.m was extremely high at 56 .mu./.mu.m (54 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 28 seconds (approximately 29 seconds).
seconds), and from this we can understand that it has sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using white light.The amount of light required was 2.3 lux seconds (2.0 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. 2 control valves (7
08) and the fourth control valve (710), hydrogen gas is supplied from the first tank (701), acetylene gas is supplied from the second tank (702), and germane gas is supplied from the fourth tank (704), respectively at the output pressure. The first under 1.0Kg/cm2,
Second and sixth flow controllers (713, 714, and 71
6) Allowed to flow into the interior. Using each flow rate controller, set the flow rate of hydrogen gas to 105,105se and the flow rate of acetylene gas to 45.
Set the flow rate of secm and germane gas to 9 sccm and mix in the middle! (731) and flowed into the reaction chamber (733) from the main pipe (732). After each flow rate stabilizes, the pressure inside the reaction chamber (733) decreases to 2.
The pressure control valve (745) was adjusted so that the pressure was 0 Torr. On the other hand, as the conductive substrate (752), an aluminum substrate of 50 mm x 50 mm x 3 mm in thickness was used.
After heating the gas to 0°C and stabilizing the gas flow rate and pressure, turn on the high frequency power source (739) that was previously connected using the connection selection switch (744), and connect the power application electrode (7
36) 90Watt power at frequency 13.56MHz
A plasma polymerization reaction was carried out for about 3 hours and 20 minutes 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 34 at % based on the total amount of carbon atoms and hydrogen atoms. Also,
According to Auger analysis, the amount of germanium atoms contained was 7.8 at % based on the total constituent atoms.

Charge generation layer forming step: Next, the first control valve (707) and the fifth control valve (711)
, and the sixth control valve (712), and the first tank (7
Hydrogen gas from 01), nitrous oxide gas from the fifth tank (705), and silane gas from the sixth tank (706) are supplied to the first, fifth, and sixth flow rate suppressors under an output pressure of IKg/cm2. (713, 717, and 718). At the same time, the fourth control valve (710) is opened, and diborane gas diluted to 1100 pp with hydrogen gas is supplied from the fourth tank (704) to the fourth tank under an output pressure of 1.5 kg/cm2.
It was made to flow into the flow rate controller (716).

Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200.
secm, nitrous oxide gas flow rate 3sec, silane gas flow rate 1001005e hydrogen gas 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) was reduced to 1.0 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 240℃ 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 45 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-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 atomic % and the boron atoms were 11 atomic ppm based on the total constituent atoms.
, oxygen atoms were 0.31 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 -900V (+970V).In other words, since the total photoreceptor film thickness is 15°3μm, the charging capacity per μm is 59V. /μm (63V/μm), which is extremely high.
From this, it was understood 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 46 seconds (approximately 49 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 7.2 lux·sec (4.5 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.

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

Example 5 Using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Control valve (70
8) and the sixth control valve (712) are released to supply hydrogen gas from the first tank (701), butadiene gas from the second tank (702), and silane gas from the sixth tank (706) to an output pressure of 1. The first, second, and sixth flow controllers (713, 714, and 718
). Using each flow rate controller, set the flow rate of hydrogen gas to 60 sec and the flow rate of butadiene gas to 60 sec.
cm and the flow rate of silane gas to 1105 cC, the main pipe (7
32) into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 2.0T.
The pressure control valve (745) was adjusted so that the

On the other hand, the conductive substrate (752) is 50 x 50 x 50 x 50 x 50 x 50 x 50
× Using an aluminum substrate with a thickness of 3 mm, heat the temperature at 130°C in advance.
After heating to , and with the gas flow and pressure stable,
Turn on the low frequency power supply (741) that has been connected in advance using the connection selection switch (744), and connect the power application electrode (736).
) was applied with a power of 180 Watts at a frequency of 100 KHz to carry out a plasma polymerization reaction for about 30 minutes to form a 15 μm thick a-C film as a charge transport layer on the conductive substrate (752). After completing the film formation, stop applying power and
The control valve was closed and the inside of the reaction chamber (733) was sufficiently evacuated.

When organic elemental analysis was performed on the a-C film obtained as described above, the amount of hydrogen atoms contained was 40 at % based on the total amount of carbon atoms and hydrogen atoms. Also,
According to Auger analysis, the amount of silicon atoms contained was 9.4 at % based on the total constituent atoms.

Charge generation layer forming step: Next, the first adjustment valve (707) and the fifth adjustment valve (711)
, and the sixth control valve (712), and the first tank (7
Hydrogen gas from the fifth tank (705), and silane gas from the sixth tank (706) are supplied to the first, fifth, and sixth flow rate controllers (713, 01) under an output pressure of IKg/am2. 717 and 718). At the same time, the fourth control valve (710) is released and the fourth tank (710) is released.
Phosphine gas diluted to 10 ppm with hydrogen gas from 04) was flowed into the fourth flow rate controller (716) under an output pressure of 1.5 Kg/am2. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 seconds, the oxygen gas flow rate to 1.3 seconds, and the silane gas flow rate to 200 seconds.
The flow rate of phosphine gas diluted to 1100pp with ecms hydrogen gas was set to 10105e, and the reaction chamber (733
). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 0.9 Torr. On the other hand, the conductive substrate (752) on which the a-C film has been completely formed is heated to 250°C, and with the gas flow rate and pressure stable, it is heated at a frequency of 13.56 MHz from a high frequency power source (739). A power of 35 Watts was applied to the power application electrode (736) to generate glow discharge. This discharge was carried out for 5 minutes, and a thick 0.
A charge generation layer of 3 μm was obtained.

The obtained a-3i film was subjected to ○NH 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 phosphorus atoms were 12 atomic ppm% of the total constituent atoms.
The oxygen atom content was 0.3 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 -890V (+930V), 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 58 .mu./.mu.m (61 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 38 seconds (approximately 41 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 2.6 lux·sec (8.9 lux・seconds), and from this it was understood that it had sufficient photosensitivity performance.

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

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

As shown in FIG. 1, using the production apparatus according to the present invention,
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. The fourth control valve (710) is released, and hydrogen gas is supplied from the first tank (701) and germane gas is supplied from the fourth tank (704) at the first and fourth flow rates under an output pressure of 1.0 Kg/cm2. It was made to flow into the controllers (713 and 716). At the same time, myrcene gas is transferred from the first container (719) to the first temperature controller (722) at a temperature of 70°C and then to the seventh flow rate controller (728).
It flowed inside. Using each flow rate controller, the flow rate of hydrogen gas is 20 seconds, the flow rate of germane gas is 5 seconds,
And the flow rate of myrcene gas was set to 5 seconds, and the main pipe (732) was passed through the intermediate mixer (731).
The liquid then flowed into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 1.5 Torr.
The pressure control valve (745) was adjusted so that on the other hand,
As the conductive substrate (752), fir 50 x paddle 50 x 43
Using an aluminum substrate of 1.0 mm in diameter, it was heated to 100°C in advance, and with the gas flow rate and pressure stabilized, the low frequency power supply (741), which had been connected in advance with the connection selection switch (744), was turned on. 1 to the power application electrode (736)
A plasma polymerization reaction was carried out for about 3 hours and 40 minutes by applying a power of 10 Watts at a frequency of 500 KHz to form a 15 μm thick a CVC 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 45 at % based on the total amount of carbon atoms and hydrogen atoms. Also,
According to Auger analysis, the amount of germanium atoms contained was 2.8 at % based on the total constituent atoms.

Charge generation layer forming step; Next, the first regulating valve (707) and the fifth regulating valve (711)
, and the sixth control valve (712), and the first tank (7
Hydrogen gas from the fifth tank (705), and silane gas from the sixth tank (706) are supplied to the first, fifth, and sixth flow restrictors (713) under an output pressure of IKg/cm2. , 717, and 718). At the same time, the fourth control valve (710) is released and the fourth tank (710) is released.
04) Do not allow the phosphine gas diluted to 10 ppm with hydrogen gas to flow into the fourth flow rate controller (716) under an output pressure of 1.5 Kg/cm2. Adjust the scale of each flow rate controller to set the flow rate of hydrogen gas to 2003 CCm and the flow rate of N oxygen gas to 0.5 sec.

The flow rate of silane gas is 200 sec, and the flow rate of hydrogen gas is 110 sec.
The flow rate of phosphine gas diluted to 0pp is 10105
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 regulating 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).
．． 40W to power application electrode (736) under 56MHz
A glow discharge was generated by applying a power of tt. This discharge was carried out for 5 minutes to obtain a charge generation layer with a thickness of 0.3 μm.

The obtained a-Si film was subjected to ○NH analysis in metal (Full EMGA-1300 manufactured by Itaba), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 23 at% of the total constituent atoms, the phosphorus atoms were 13 at ppm,
The oxygen atom content was 0.1 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 -430V (+620V), 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 28 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 19 seconds (approximately 27 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 1.1 lux·sec (2.9 lux・seconds), and from this it was understood that it had sufficient photosensitivity performance.

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

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

[Brief explanation of the drawing]

1 to 6 are drawings showing the structure of a photoreceptor according to the present invention, and FIGS. 7 to 8 are drawings showing an apparatus for manufacturing a photoreceptor according to the invention. Applicant: Minolta Camera Co., Ltd. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Procedural amendment October 21, 1985 Commissioner of the Patent Office Kunio Ogawa 2 Name of the invention Photoconductor 3 , Relationship with the case of the person making the amendment Applicant address Z-30, Azuchi-cho, Higashi-ku, Osaka City Name of Osaka Kokusai Building (607) Minolta Camera Co., Ltd. Voluntary amendment 5, Drawing subject to amendment 6, Details of amendment Drawing 8 Correct as shown in "Corrected Figure 8".

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 one of silicon atoms and germanium atoms, and the charge generation layer is a hydrogenated amorphous silicon film containing oxygen atoms and at least one of phosphorus atoms and boron atoms, or a fluorinated amorphous silicon film containing oxygen atoms and at least one of phosphorus atoms and boron atoms. A photoreceptor characterized by being an amorphous silicon film.