JPS6382484A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain stable and excellent photoconductive characteristics by using a hydrogenated amorphous carbon film contg. Si atoms or Ge atoms as an electric charge transfer layer and hydrogenated amorphous SiGe film contg. specific atoms as an electric charge generating layer. CONSTITUTION:The photosensitive body is constituted by laminating the charge transfer layer 2 and the charge generating layer 3 successively on a conductive substrate 1. The layer 2 in this constitution consists of the hydrogenated amorphous (a-)carbon film contg. at least either of the Si atoms or Ge atoms. The layer 3 consists of the hydrogenated a-SiGe film contg. carbon atoms and contg. at least either of the phosphorus atoms or boron atoms or the similar fluorinated a-SiGe film. Adequate transferability is thereby provided to the layer 2 and further, excellent electrophotographic performances such as electrical chargeability, durability, weatherability, and environmental staining resistance are provided thereto. The layer 3 is extremely thin in film thickness and has the excellent photoconductivity to visible light or wavelength near semiconductor laser light.

Description

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

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

The main electrophotographic photoreceptor materials conventionally used include inorganic substances such as amorphous selenium, selenium arsenide, selenium telluride, cadmium sulfide, zinc oxide, amorphous silicon, polyvinyl carbazole, metal phthalocyanine,
Examples include organic substances such as disazo pigments, trisazo pigments, perylene pigments, triphenylmethane compounds, triphenylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, oxazole compounds, and oxadiazole compounds. In addition, its structural forms 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 an 81-layer 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, but all of the inorganic substances, except for the amorphous gas 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, which can be 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, the film formation rate is slow, and as the film formation time increases, explosive silane undecomposed products are generated in the form of powder, and there are many other inconveniences in production. Furthermore, if this dust gets mixed into the photosensitive layer during manufacturing, it will have a significant negative effect on image quality. Generally speaking, amorphous silicon originally has a high dielectric constant and therefore has low charging performance, and in order to charge it to a predetermined surface potential in a copying machine, it is necessary to increase the thickness of the film, making it difficult to use an expensive amorphous silicon film. It must be allowed to accumulate for a long 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.
1 of Applied P.

lymer Sc 1ence) Volume 17, No. 885
Pages 892 to 892, it is also reported by the same author in 1979 that any organic compound can be prepared from gas.
American Chemical Society (Amer)
ican Chemical Society)
Polymerization), its film formability is also discussed.

However, plasma organic polymer films prepared by conventional methods are used only for applications that assume insulation properties, that is, they are considered to be insulating films with a specific resistance of about 1016 Ωcm, like ordinary polyethylene films, or was used with the understanding that it was at least such a membrane. Due to the same recognition, its actual use in electrophotographic photoreceptors has been limited to protective layers, adhesive layers, blocking layers, or insulating layers, and has only been used as so-called undercoat layers or overcoat layers.

For example, JP-A-59-28161 discloses a photoreceptor in which a plasma-polymerized polymer layer having a network structure is provided on a substrate as a blocking layer and an adhesive layer, and an amorphous silicon layer is provided on the polymer layer. ing. Japanese Patent Application Publication No. 5
Publication No. 9-38753 discloses that 10 to 100 plasma polymerized films with high resistance of 1013 to 1015 Ωcm, which can be generated from a mixed gas of oxygen, nitrogen, and hydrocarbons, are formed on a substrate as a blocking layer and an adhesive layer, and then an amorphous film is formed. A photoreceptor provided with a silicon layer is disclosed. 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-Si
However, it does not solve the above-mentioned essential problems.

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

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

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

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

Philosophical Magazine (Philosophical Magazine) published in 1976 by
Since it was reported in Vol. 33, pages 935 to 949 of I Magaz 1ne) that it is a material whose polarity can be controlled, attempts have been made to apply it to various photoelectric devices. Regarding application to photoreceptors, for example, JP-A-56-62254, JP-A-57-119356, JP-A-57-177147, JP-A-57-
119357, JP 57-177149, JP 57-119357, JP 57-17
7146, JP 57-177148, JP 57-174448, JP 57-1744
No. 49, JP-A-57-174450, etc.
Amorphous silicon photoreceptors containing carbon and carbon atoms have been disclosed, but all of them are aimed at adjusting the photoconductivity of amorphous silicon with carbon atoms, and amorphous silicon itself requires a thick film. It is said that

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

While considering the application of amorphous carbon films to electrophotographic photoreceptors, the present inventors discovered that hydrogenated amorphous carbon films, which were originally thought to be insulating, were capable of forming at least one of silicon atoms and germanium atoms. By containing , it has charge transport properties and is easily stacked with a hydrogenated or fluorinated amorphous silicon germanium film containing at least one of phosphorus atoms and boron atoms and also carbon atoms. It has been found that the material begins to exhibit suitable electrophotographic properties. There are many unclear points in the theoretical interpretation, even for the present inventor, and it is not possible to discuss it in detail. A band structure formed by electrons in an unstable energy state, such as π electrons, unpaired electrons, and free radicals, contains at least one of phosphorus atoms and l atoms, and also contains carbon atoms. Since the hydrogenated or fluorinated amorphous silicon germanium film has a similar energy level in the conduction band or valence band to the band t11 formed by the film, it contains at least one of phosphorus atoms and boron atoms and also contains carbon atoms. Carriers generated in the hydrogenated or fluorinated amorphous silicon germanium film containing silicon atoms can be easily injected into the hydrogenated amorphous carbon film containing at least one of silicon atoms and germanium atoms. It is presumed that this is because the electrons can travel suitably through 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.

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 carbon atoms. Another object of the present invention is to provide a photoreceptor using a fluorinated amorphous silicon germanium layer as a charge generation layer.

In order to solve the problem, 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 silicon atoms and germanium atoms generated from a plasma polymerization reaction. hydrogenated or fluorinated amorphous silicon germanium, in which the charge generation layer contains at least one of phosphorus atoms and boron atoms, and carbon atoms; The present invention relates to a photoreceptor characterized in that it is a film (hereinafter, the charge transport layer according to the present invention is referred to as an a-C film and the charge generation layer is referred to as a-SillJ).

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 created 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 germanium film containing at least one of phosphorus atoms and hydrogen atoms and carbon 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. .

In addition, the charge generation layer has excellent TJ photoconductivity for visible light or light with wavelengths near semiconductor laser light, and has an extremely thin film thickness compared to conventional amorphous silicon photoreceptors. It is something that can be put to good use.

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

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

There are many types of hydrocarbons that can be used, but examples of saturated hydrocarbons include methane, ethane, propane, butane,
Pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane,
Tocosan, Tricosan, Tetracosan, Pentacosan 1
, hexacosane, heptacosane, octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, etc., as well as isobutane, isopentane, neopentane, -(sohexane,
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-)dimethylpentane, 2.
Isoparaffins such as 2,4-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-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, cyclobencune, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, and the like. cycloparaffins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, and cycloolefins such as limonene, tervirun, phelandrene, sylvestrene, thuen, carene, pinene, bornylene, kanghuen, fuenchen, Terpenes such as cycloundecane, tricyclene, bisabolene, zingiberene, curcumene, humulene, kajinensesquivenichen, selinene, caryosirene, santarene, cedrene, campholene, phylloclatene, bodocarbrene, mirene, and steroids are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, pseudocumene, mesitylene, prenitene, isodurene, durene,
Pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, biphenyl, terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

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

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

The amount of hydrogen atoms contained in the a-C film in the present invention 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
0 ums, particularly 7 to 20 um, is suitable; if it is thinner than 5 μm, sufficient copying image density cannot be obtained because the charging potential is low. Moreover, if it is thicker than 5011 m, 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 a-CM from a raw material gas in the present invention includes a method in which the raw material gas is formed through a plasma state generated by a plasma method using direct current, low frequency, high frequency, microwave, etc. Most preferably, it may also be formed through an ion state generated by ionization vapor deposition, ion beam vapor deposition, etc., or from neutral particles generated by vacuum vapor deposition, sputtering, etc. It may be formed completely, or it may be formed by a combination of these.

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 t-th state of the silicon compound or germanium compound does not necessarily have to be in a gas phase at normal temperature and pressure, but can be melted, evaporated, or evaporated by heating or reduced pressure.
As long as it can be vaporized through sublimation or the like, it can be used in either liquid or solid phase. As the silicon compound or germanium compound, for example, undefeated compounds such as silane, disilane, fluorinated silane, and 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 can be determined by a conventional method of elemental analysis, such as Auger analysis. If the film does not contain silicon atoms or germanium atoms, 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%, the silicon atoms, which had guaranteed suitable transport properties when added in small amounts, instead exhibit the effect of increasing the resistance of the film, resulting in a decrease in sensitivity. . On the other hand, when the amount of germanium atoms exceeds 10 at %, the germanium atoms, which had guaranteed suitable transport properties when added in small amounts, conversely work to lower the resistance of the film, and the charging ability decreases. It ends up. Therefore, the range of the amount of silicon atoms or germanium atoms added in the present invention 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 increase the amount of silicon atoms or germanium atoms added to the a-C film according to the present invention. If the amount of the compound introduced can be reduced, 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. In addition, phosphine gas, diborane gas, or the like is used as a raw material gas for containing phosphorus atoms or boron atoms as chemical 113 decorative substances in the film. Furthermore, raw n gases for incorporating carbon atoms into the film as chemical modifiers include methane, ethane, ethylene, acetylene, propane, propylene, butane, butadiene, butadiyne, butene, carbon oxide, or carbon dioxide. A carbon compound gas such as carbon is used. Furthermore, gel and mangas are used to contain germanium atoms.

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

In the present invention, the amount of phosphorus or boron atoms contained as a chemical modifier is -C20000 with respect to all constituent atoms.
It is less than atomic ppm. Here, the content of phosphorus atoms or boron 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 phosphorus atoms or boron atoms in the film is higher than 20,000 atomic ppm, the phosphorus atoms or boron atoms that have guaranteed suitable transport properties or polar printing area effects when added in small amounts, On the contrary, it has 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 single atoms added in the present invention is important.

In the present invention, the amount of carbon atoms contained as a chemical modifier is 0.001 to 5 at% based on the total constituent atoms.
It is. Here, the content of carbon 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 carbon atoms in the film is lower than 0.001 at%, the electrical resistance value of the a-5i film becomes low, making it difficult for the a-5i film to be subjected to electric fields due to corona charging, etc., and photoexcited carriers are Not necessarily efficient<a-CM'A
This results in a decrease in sensitivity. Furthermore, the charging ability is also reduced. When the content of carbon atoms in the film is higher than 5 at %, the electrical resistance value of the a-3i film becomes too high, resulting in a decrease in sensitivity due to a decrease in the generation efficiency of photoexcited carriers and a decrease in the mobility speed of carriers. invite Therefore, the range of the amount of carbon 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 can be approximately 10 to 35 at%. Here, the content of hydrogen atoms or fluorine atoms in the film can be determined by using conventional methods of elemental analysis, such as ONH analysis and Auger analysis.

The appropriate thickness of the a-Si film as the charge generation layer in the present invention is 0.1 to 5 um for use in a normal electrophotographic process, and if it is thinner than 0.1 um, light absorption is insufficient. As a result, sufficient charge generation is not performed, leading to a decrease in sensitivity. Moreover, if it is thicker than 5 μm, it is not preferable in terms of productivity. This a-5i film has a rich charge generation ability,
Furthermore, in the fine Ntg formation 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 a-Sii from the raw material gas in the present invention is carried out in the same manner as the case of forming an a-C film.

In the present invention, the amount of carbon atoms, phosphorus atoms, or boron atoms contained as chemical modifiers is mainly determined by the amount of carbon compound gas, phosphine gas, or diborane gas introduced into the reaction chamber in which the plasma reaction is performed. It can be controlled by increasing or decreasing the amount of introduced. By increasing the amount of carbon compound gas, phosphine gas, or diborane gas introduced, carbon atoms, phosphorus atoms,
Alternatively, it is possible to reduce the amount of q1 atoms added, and conversely, if the amount of carbon compound gas, phosphine gas, or diborane gas introduced is reduced, the aS+&
It is possible to reduce the amount of carbon atoms, phosphorus atoms, or boron atoms added therein.

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). Figure 2 1. As another form of t1, a structure is shown in which a charge generation layer (3) and a charge transport layer (2) are sequentially laminated on a conductive group Vj, (1). FIG. 3 shows a conductive substrate (1) as another form.
, a structure in which a charge transport layer (2), a charge generation layer (3), and a charge transport layer (2) are sequentially laminated on the top.

When the surface of the photoreceptor is positively charged using a corona charger or the like and then used for image exposure, in FIG. 1, holes generated in the charge generation layer (3) pass through the charge transport layer (2). Electrons travel toward the conductive substrate (1), and in Figure 2, electrons generated by charge generation N (3) travel through the charge transport layer (2) toward the surface of the photoreceptor; Holes generated in the layer (3) travel toward the conductive substrate (1) through the charge transport layer (2) on the conductive substrate side, and at the same time travel through the charge generation layer (2) toward the conductive substrate (1).
The electrons generated in step 3) travel toward the surface of the photoreceptor through the charge transport layer (2) on the surface side, resulting in a static 7.
! 1 latent image is formed. On the other hand, when the surface of the photoreceptor is negatively charged and then used for image exposure, the behavior of electrons and holes can be exchanged to understand the mobility of carriers. In FIGS. 2 and 3, the irradiation light for image exposure passes through the charge transport layer, but since the charge transport layer according to the present invention has excellent translucency, it forms a suitable latent image. Is possible.

FIG. 4 shows, as a further embodiment, a charge transport layer (2), a charge generation layer (3) and a surface protective layer (
4) is shown in a structure formed by sequentially stacking them. In other words, it corresponds to the form shown in Fig. 1 with a surface protective layer provided, but
In the form shown in FIG. 1, since the outermost surface is an a-Si film with poor moisture resistance, it is preferable to provide a surface protective layer in order to ensure practical humidity stability in the case of multilayer film.
In the case of the configurations shown in Figures and Figure 3, the outermost surface is a with excellent durability.
- Since it is CFL, there is no need to provide a surface protective layer, but
For example, a surface protective layer may be provided for the purpose of adjusting compatibility with various elements within a copying machine, such as preventing staining of the photoreceptor surface 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.
sequentially 'f! This figure shows a four-layered structure. In other words, it corresponds to the form shown in Fig. 2 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, so in most cases adhesiveness and injection prevention are required. It is preferable to provide an intermediate layer to ensure the effect. 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 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 (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 the gas phase by discharge under reduced pressure, and diffuses active neutral species or charged particles contained in the generated plasma atmosphere onto the substrate, using electric force or magnetism. It is preferable that the particles be generated by a so-called plasma polymerization reaction, in which the particles are 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 1st to 6th school 'M# Sin Vessel (713)~
(718). In the figure (719)・～(7
21) are first to third containers containing raw material compounds that are in a liquid or solid phase at room temperature, and each container is heated to a temperature given by the first to third YJ devices (722) to (724) for vaporization. It can be heated, and each container is roughly 7th to 9th.
It is connected to control valves (725) to (727) and seventh to ninth flow rate controllers (728) to (730). These gases are mixed in a mixer (731) and then passed through the main pipe (732).
) into the reaction chamber (733). The pipes along the way can be heated by appropriately placed pipe heaters (734) so that the gas, which is the vaporized raw material compound that is in a liquid or solid state at room temperature, does not condense on the way. . In the reaction chamber, a grounding voltage tN (735) and a power applying Ti electrode (736) are installed facing each other, and each electrode can be heated by an electrode heater (737). The power application type w1 (736) has a matching box for high frequency power (7
38) and matching for high frequency power (739) and low frequency power! A low frequency power supply (741L) is connected to a DC power supply (743) through a low-pass filter (742) via (740), and it is possible to apply power for different numbers of liquids using a connection selection switch (744). .Reaction chamber (73
3) The pressure inside can be TA'J by the pressure sub-part valve (745), and the pressure inside the reaction chamber (733) can be reduced through the exhaust system selection valve (746), diffusion pump (747), oil rotary Pump (748) or cooling exclusion device (749)
, mechanical booster pump (750), and oil rotary pump (748). Regarding exhaust gas,
After making it safe and harmless using a suitable exclusion device (753), it is exhausted into the atmosphere. These exhaust system piping can also be heated by appropriately placed piping heaters (734) to prevent the vaporized gas from the raw material compound, which is in a liquid or solid phase at room temperature, from condensing on the way. ing. For the same reason, the reaction chamber (733) can also be heated by the reaction chamber heater (751), and
The conductive substrate (752) on the electrode is now installed. In Fig. 7, the conductive substrate (752) is connected to the ground '7t1 pole (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 7oO series with the 800 series. In FIG. 8, the reaction chamber (83
3) A cylindrical conductive substrate (852) that also serves as the ground electrode (735) in FIG. 7 can be installed inside, and an electrode heater (837) is arranged inside. Conductive substrate (
852) There is also a cylindrical power application electrode (
836) is arranged, and an electrode heater (837) is arranged on the outside. The conductive substrate (852) is rotatable using an external drive motor (854).

The reaction chamber used for photoreceptor production is preliminarily heated by a diffusion pump.
The pressure is reduced to approximately o-4 to 10-' Torr, and the degree of vacuum is confirmed and the gas adsorbed inside the apparatus 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 starts 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, h-staining 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, if a charge generation layer or an overcoat layer is required in the desired photoreceptor configuration, this device can be used as is, or the vacuum can be broken and removed and transferred to another device to coat these layers. established,
A photoreceptor according to the present invention is obtained.

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. 7, first, the inside of the reaction device (733) is brought to a high vacuum of about 10-6 Torr, and then the first control valve (70?) and 4th FJJ
The control valve (710) is released, and hydrogen gas is supplied from the fourth tank (701) and germane gas is supplied from the fourth tank (704) to an output pressure of 1. It was made to flow into the first and fourth flow rate controllers (713 and 716) under ○Kg/cm2. At the same time, myrcene gas is supplied from the first container (719) to the first temperature controller (722) and then to the seventh flow rate control valve (728) at a temperature of 70°C.
It flowed inside. Each flow rate system? Using the M device, the flow rate of hydrogen gas was 20 sec, and the flow rate of germane gas was 5 sec.
, and the flow rate of myrcene gas is set to 20 seconds, 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 1.5To
The pressure regulating valve (745) was adjusted so that rr. On the other hand, as the conductive substrate (752), fir 50X paddle 50X
Using an aluminum substrate with a thickness of 3 mm, preheat it to 150°C, and when the gas flow rate and pressure are stable, turn on the low frequency power supply ('741) that was previously connected using the connection selection switch (744). and the power application electrode (736
) was applied with a power of 110 Watts at a frequency of 500 KHz to perform a plasma polymerization reaction for about 3 hours and 40 minutes to form a 15 μm thick a-C film as a charge fh 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-C film obtained as described above revealed that the amount of home atoms contained was 45 atomic % based on the total amount of carbon atoms and hydrogen atoms. Moreover, the amount of germanium atoms contained was 2.8 at % based on the total constituent atoms according to Auger analysis.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
releasing the second control valve (708), the third control valve (709), the fifth control valve (711), and the sixth control valve (712);
Hydrogen gas from the first tank (701), hydrogen gas from the second tank (70
2), germane gas from the third tank (703), tetrafluoride silane gas from the fifth tank (705), and silane gas from the sixth tank (706) under an output pressure of IKg/am2. 1st, 2nd, 3rd, 5th, and 6th flow rate system (collocation (713, 714, 715, 717,
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/am2;
I let it flow in. Adjust the scale of each flow rate control i-usage to set the hydrogen gas flow rate to 200 sec and the germane gas flow rate to 3 sec.
cm.

The flow rate of silane tetrafluoride gas is 50 seconds, the flow rate of carbon tetrafluoride gas is O, lsec, and the flow rate of silane gas is 50 seconds.
ecm, the flow rate of diborane gas diluted to 1100 pp with hydrogen gas was set to 1103 CC, and the diborane gas was allowed to flow into the reaction chamber (733). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 0.9 Torr. On the other hand, a-C
The conductive substrate (7.52) on which the film is formed is 250
℃, and with the gas a, amount and pressure stable, a frequency of 13656 MHz is supplied from a high frequency power source (739).
d'), apply W force mJEj (736) to 35W
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 063 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 22 at% of the total constituent atoms, and the boron atoms were 11 at ppm.
%Fluorine atoms are 4.8 at%, carbon atoms are 0.1 at%,
Germanium atoms were 6.4 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 at the time of positive charging are shown in parentheses, and the highest charging potential is -480V (+530V), 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 31 .mu.m/.mu.m (35 V/.mu.m).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 16 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, white light was used to decay the surface potential to 20% of the highest charging potential, and the required amount of light was 1. flux-second (1.5 lux-second), and from this it was understood that it had sufficient photosensitivity performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using semiconductor laser light (emission wavelength 780 nm).The required light amount was 9.3e.
rg/cm2 (8.2 erg/am2), and from this it was concluded that it had sufficient long wavelength light sensitivity performance.

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

In addition, when an image was formed and transferred to this photoreceptor using the commonly used Carlson process, the result was 5! 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. 7, first, the inside of the reaction device (733) is brought to a high vacuum of about 10-6 Torr, and then the first control valve (707) and the second control valve (708
), and the sixth regulating valve (712) are released, and the first tank (
701), ethylene gas from the second tank (702), and silane gas from the sixth tank (706), each at an output pressure of 1. It was made to flow into the first, second, and sixth flow rate controllers (713, 714, and 718) under ○Kg/cm2. Using each flow rate controller, set the flow rate of hydrogen gas to 60 sec, the flow rate of ethylene gas to 60 SCCm, and the flow rate of silane gas to 3 sec. The liquid then entered 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 1.8 Torr. On the other hand, as the conductive substrate (752), use an aluminum substrate measuring 50 mm wide x 50 mm wide x N3 mm, heat it in advance to 250°C, and with the gas flow rate and pressure stable, connect the connection selection switch ( Turn on the high frequency power supply (739) connected by
Plasma polymerization reaction was carried out for about 10 hours by applying the voltage under MHz, and a 15 μm thick a-
A C film was formed as a charge transport layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

When organic elemental analysis was performed on the a-C film obtained as described above, the amount of hydrogen atoms that could be contained was 45 at % based on the total amount of carbon atoms and hydrogen atoms. Furthermore, according to Auger analysis, the amount of silicon atoms contained was 0.4 atomic % based on the total constituent atoms.

Charge transport layer forming step: Next, some of the tanks were replaced, and the first control valve (7o7)
The second control valve (708), the fifth control valve (711), and the sixth control valve (712) are released, hydrogen gas is released from the first tank (701), germane gas is removed from the second tank (702),
Methane gas from the fifth tank (705) and silane gas from the sixth tank (706) are supplied to the first, second, fifth, and sixth flow rate controllers (713,
714, 717, and 718).

At the same time, the fourth control valve (710) is released and the fourth tank (
Phosphine gas diluted to 10 ppm with hydrogen gas (704) was allowed to flow into the fourth flow rate control t'liu (716) under an output pressure of 1.5 Kg/cm2. Each style ff
Adjust the scale of the i-controller to set the hydrogen gas flow rate to 200se.
cm, germane gas flow rate 68 CCm, methane gas flow rate 3 sec, silane gas flow rate 200 sec
The flow rate of phosphine gas diluted to 1100 pp with hydrogen gas was set to 10105e, and the flow rate was allowed to flow into the reaction chamber (733). After each flow rate stabilized, the reaction chamber (73
3) The pressure inside 1. The pressure control valve (745) was adjusted so that the pressure was ○Torr. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 230°C.
With the gas flow rate and pressure stable, turn on the high frequency power supply (73
9) Frequency v1.13.

35W to the power application electrode (736) under 56MHz
A power of t 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-Si film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 18 at% of the total constituent atoms, and the phosphorus atoms were 12 at ppmN
Carbon atoms are 0.3 at%, germanium atoms are 10.4
It was atomic%.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -490V (+740V), 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 (48 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 12 seconds (approximately 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, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential.The amount of light required was 1.2 lux·sec (3.5 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.

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 an N charge blocking layer were provided on the head.

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Release the second control valve (708) and the sixth control valve (712),
Hydrogen gas from the first tank (701), hydrogen gas from the second tank (70
Butadiene gas from 2) and silane gas from the sixth tank (706) flow into the first, second, and sixth flow rate controllers (713, 714, and 718) under an output pressure of 1.0 Kg/am2, respectively. It's gone. Using each flow rate controller,
The flow rate of hydrogen gas was set to 60 seconds, the flow rate of butadiene gas was set to 60 seconds, and the flow rate of silane gas was set to 5 seconds, and the mixture was passed through an intermediate mixer (731).
It flowed into the reaction chamber (733) from the main pipe (732).

After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 1.8 Torr. On the other hand, as the conductive substrate (752), fir 5
Using an 0XI50X aluminum substrate with a thickness of 3 mm, preheat it to 250°C, and when the gas flow rate and pressure are stable, turn on the low frequency power supply (741) that was previously connected using the connection selection switch (744). and power application f
Power of 120Watt to fi rod (736) at frequency 40
A plasma polymerization reaction was performed for about 40 minutes under 0 KHz, and a 15 μm thick a-
A C film was formed as a charge transport layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

When organic elemental analysis was performed on the a-C film subjected to t4 as described above, the amount of hydrogen atoms that could be contained was 53 at % based on the total amount of carbon atoms and hydrogen atoms. Furthermore, from Auger analysis, the amount of silane atoms contained is total t
The amount was 5.2 at% based on the R atoms.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
The second control valve (708), the fifth control valve (711), and the sixth control valve (712) are released, hydrogen gas is released from the first tank (701), germane gas is removed from the second tank (702),
Methane gas from the fifth tank (705) and silane gas from the sixth tank (706) are supplied to the first, second, fifth, and sixth flow rate controllers (713,
714, 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 rate controller (716) under an output pressure of 1.5 Kg/cm2. Each flow rate control IJN
Adjust the scale to set the hydrogen gas flow rate to 200 sec, the germane gas flow rate to 6 sec, and the methane gas flow rate to O.
, Olsecm.

The flow rate of silane gas is 101005a, and the flow rate of hydrogen gas is 110a.
Rare to 0pp? , the flow rate of the broken diborane gas is 10105
e, and do not allow it to flow into the reaction chamber (733). After each flow rate stabilized, the pressure was adjusted so that the pressure in the reaction chamber (733) was 0.8 Torr, # (7
45) was adjusted. On the other hand, the conductive substrate (752) on which the a-C film is formed is heated to 250°C, and the high-frequency power source (739) is heated to stabilize the gas flow rate and pressure.
Power application type +Eii under frequency 13.56MHz
(736) was applied with a power of 35 Watts to generate a glow discharge. This discharge was carried out for 5 minutes, and a thickness of 0°3 μ
A charge generation layer of m was obtained.

The obtained a-Si film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 20 at% of all constituent atoms, and 1M elementary atoms were 9 at pPm.
% carbon atoms is 0. ○01 atomic%, germanium atoms are 9
．． It was 8 atom%.

Characteristics: The resulting photoreceptor can be negatively charged or positively charged in the commonly used Carlson process. When used in g-den, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -580V (+610V).In other words, since the total photoreceptor film thickness is 15°3um, the charging ability per 1μm is 38V. /μm (40V/um), which was extremely high, and it was understood from this that it had sufficient charging performance.

In addition, the time required for dark decay from Vmax to 90% of Vmax in the dark was approximately 23 seconds (approximately 25 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, the brightness was attenuated to a surface potential of 20% of the highest charging potential using white light.The amount of light required was 1.6 lux seconds (1.5 lux・seconds), and from this we can understand that it has sufficient photosensitivity performance. Also, after initial charging to the highest charging potential, what was the amount of light required to attenuate the brightness to a surface potential of 20% of the highest charging potential using semiconductor laser light (emission wavelength 780 nm)? ,8e
rg/cm': (9.7 erg/crn2), and from this it was understood that it had sufficient long wavelength light sensitivity 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.

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) are released, 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. 1st under 1.0Kg/am2
, 2nd, and 6th flow rate control ('III device (713, 714
, and 716). Using each flow rate controller, set the flow rate of hydrogen gas to 10105sec, the flow rate of acetylene gas to 45sec, and the 'fC amount of germane gas to 9.
secm, and mixer (731)
It flowed into the reaction chamber (733) from the main pipe (732) through the main pipe (732). After each flow rate is stabilized, the reaction chamber (733)
Pressure regulating valve (7) so that the internal pressure is 2.0 Torr.
45) was adjusted. On the other hand, as the conductive substrate (752), use an aluminum substrate of 50 mm x 50 mm x 3 mm in thickness, heat it to 190°C in advance, and when the gas flow rate and pressure are stable, connect the connection selection switch (744). ) is connected to the high frequency power source (739), and a power of 90 Watt is applied to the power application electrode (736) at frequency 1.
A plasma polymerization reaction was performed for about 3 hours and 20 minutes by applying a frequency of 3.56 MHz, and a thick layer of 15 MHz was applied on the conductive substrate (752).
A μm a-C film 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 (73
3) The inside was sufficiently evacuated.

When organic elemental analysis was performed on a CH'A obtained as described above, the amount of hydrogen atoms contained was 34 at % based on the total amount of carbon atoms and hydrogen atoms.

Furthermore, the amount of germanium atoms contained was found to be 7.8 at% based on the total constituent atoms according to Auger analysis.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
The fifth control valve (711) and the sixth control valve (712) are released, and hydrogen gas is discharged from the first tank (701), germane gas from the second tank (702), ethane gas from the fifth tank (705), and Silane gas is supplied from the 6th tank (706) to the 11th, 2nd, 5th, and
and the sixth flow control device (713, 714, 717, and 7
18) Inflow into the inside. At the same time, the fourth control valve (710)
110 with hydrogen gas from the fourth tank (704).
Diborane gas diluted to 0pp, output pressure 1.5Kg
/am2 into the fourth flow controller (716). Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 seconds.

The flow rate of germane gas is 10105e, the flow rate of ethane gas is 3 sec, and the flow rate of silane gas is 1003 CCm.
The flow rate of diborane gas diluted to 1100 pp with hydrogen gas was set to 10105e and allowed to flow into the reaction chamber (733). After each flow rate stabilizes, the reaction chamber (733
) so that the pressure inside the pressure control valve (
745) was adjusted. On the other hand, the conductive substrate (752) on which the a-C film has been formed is heated to 240°C, and the high-frequency power source (739) is heated with the gas flow rate and pressure stable.
) under a frequency of 13.56 MHz from the power applying electrode (7
36) was applied with a power of 45 Watt 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.

ONH analysis in metal (
EMGA-1300 (manufactured by Itaba Seisakusho), Auger analysis, and IMA analysis revealed that hydrogen atoms contained were 21 atoms and 96 atoms, boron atoms were 11 atoms ppm, and carbon atoms f0.3 at%. , germanium atoms were 15.7 at%.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values when positively charged are shown in parentheses, but is it the best? tf electric power is -800V (+780V), that is, the total photoreceptor film thickness is 15°3μm, so it is 1μm.
The charging performance per charge was extremely high at 52 V/μm (51 V/μm), and from this it was understood that the battery had sufficient charging performance.

In addition, the time required for the dark decay from Vmax to 9% of Vmax in the dark was approximately 31 seconds (approximately 35
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.・seconds), and from this it was understood that it had sufficient photosensitivity performance.

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

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

Implementation A: 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(
708) and the sixth control 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) to an output pressure of 1. 1st under 0Kg/cm2,
Second and sixth flow controllers (713, 714, and 71
8) It flowed inward. Using each flow rate prick device, the flow rate of hydrogen gas was 60 sec, and the flow rate of butadiene gas was 603 sec.
CCm and the flow rate of silane gas were set to 1105 CC, and the gas flowed into the reaction chamber (733) from the main pipe (732) via an intermediate mixer (731). 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 ○Torr. On the other hand, as the conductive substrate (752), an aluminum substrate measuring 50 mm long x 50 mm wide x 3 mm thick was used.
After heating the gas to 0°C and stabilizing the gas flow rate and pressure, turn on the low frequency power supply (741) that was previously connected using the connection selection switch (744), and connect the power application electrode (744).
36) at a frequency of 100 KHz to perform a plasma polymerization reaction for about 30 minutes to form 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 40 at % based on the total amount of carbon atoms and hydrogen atoms. Moreover, the amount of silicon atoms contained was 9.4 at % based on the total constituent atoms according to Auger analysis.

Charge generation layer forming step: Next, some of the tanks are replaced, and the first control valve (707),
The second control valve (708), the fifth control valve (711), and the sixth control valve (712) are released, hydrogen gas is released from the first tank (701), germane gas is removed from the second tank (702),
Methane gas is supplied from the fifth tank (705) and silane gas is supplied from the sixth tank (706) at an output pressure of 'IKg/cm2.
The first, second, fifth, and sixth flow rate control formulas (713
, 714, 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 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 200 sec, the germane gas flow rate to 6 scCm, and the methane gas flow rate to 10 scCm.
105e, the flow rate of silane gas is 1001005e, the flow rate of diporane gas diluted to 1100pp with hydrogen gas is 1
01005e and flowed into the reaction chamber (733). After each flow rate stabilizes, the pressure regulating valve (745) is adjusted so that the pressure in the reaction chamber (733) becomes 0.8 Torr.
) was adjusted. 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. Power application amount tN (736
) was applied with a power of 40 Watts 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-5i film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 24 at.% of the total constituent atoms, and the boron atoms were 95 at.ppm.
, carbon atoms are 1.0 at%, germanium atoms are 10.
It was 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 -990V (+945V), 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 65 V/.mu.m (62 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 41 seconds (approximately 42 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, and the amount of light required was 6.3 lux · seconds (4.3 lux · seconds), and from this it is understood that it has sufficient photosensitivity performance.

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

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

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