JPS6382455A - Photosensitive body - Google Patents

Abstract

PURPOSE:To improve the transferability of an electric charge transfer layer by using the charge transfer layer consisting of hydrogenated amorphous carbon contg. Si or/and Ge and an electric charge generating layer contg. specific atoms together with nitrogen atoms. CONSTITUTION:For example, the charge transfer layer 2 and the charge generating layer 3 are successively laminated on a conductive substrate 1. The layer 2 consists of the hydrogenated amorphous carbon film contg. Si or/and Ge. The layer 3 consists of the hydrogenated or fluorinated amorphous silicon film contg. N and further contg. P or/and B. The layers 2, 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 additional reduction in the film thickness of the charge generating layer is permitted as well.

Description

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

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

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

However, the electrophotographic photoreceptor materials conventionally used each have drawbacks. One of these concerns is its toxicity to the human body, but with the exception of the amorphous silicon mentioned above, all inorganic substances have unfavorable properties. In order to be used, it is necessary to maintain stable performance at all times even when exposed to harsh environmental conditions such as charging, exposure, development, transfer, static elimination, and cleaning. Both had 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. I have to write the timetable VI.

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 produced 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 cannot be used as insulation films with a resistivity of about <10'6 Ωcm, like ordinary polyethylene films. or at least it was used with the recognition that it was such a membrane. Due to the same recognition, its actual use in electrophotographic photoreceptors has been limited to protective layers, adhesive layers, blocking layers, or insulating layers, and has only been used as so-called undercoat layers or overcoat layers.

For example, JP-A-59-28161 discloses a photoreceptor in which a plasma-polymerized polymer layer having a network structure is provided on a substrate as a blocking layer and an adhesive layer, and an amorphous silicon layer is provided thereon. ing. Japanese Patent Application Publication No. 5
Publication No. 9-38753 discloses that 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 has been disclosed. Tokukai Akira! 59
Publication No. 136742 discloses a photosensitive material in which a carbon film of about 1 to 5 um is formed on the surface of the substrate as a protective layer to prevent aluminum atoms from diffusing into the amorphous silicon layer provided on the aluminum substrate during light irradiation. The body is revealed. Japanese Unexamined Patent Publication No. 60-63541 discloses a photosensitive material in which a diamond-like carbon film with a thickness of 200 to 2 μm is provided in the middle as an adhesive layer in order to improve the adhesion between an aluminum substrate and an amorphous silicon layer provided thereon. It is said that the thickness of M is preferably 2 .mu.m or less from the viewpoint of the body being fully disclosed and the residual charge.

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

For example, Japanese Patent Application Laid-Open No. 50-20728 discloses that a polymer film of 0.1 to 1 μm formed by glow discharge polymerization is applied as a protective layer on the surface of a polyvinylcarbazole-selenium photoreceptor.
A photoreceptor is disclosed. Japanese Patent Publication No. 59-214
Japanese Patent No. 859 discloses a technique for forming a film of about 5 μm on the surface of an amorphous silicon photoreceptor by plasma polymerizing an organic hydrocarbon monomer such as styrene or acetylene as a MN. 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 thickness M is preferably 2 μm or less from the viewpoint of light transmission. ing.

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

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

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

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

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

As mentioned above, plasma organic polymer films conventionally used in electrophotographic photoreceptors have been used as so-called undercoat layers or overcoat layers; It is a membrane that does not require a transport function, and is used based on the judgment that organic polymer membranes are 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 for thin crotches that can be used. 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 nitrogen 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 nitrogen atoms. Therefore, carriers generated in the hydrogenated or fluorinated amorphous silicon film containing at least one of phosphorus atoms and boron atoms and nitrogen 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 travel suitably through the membrane.

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 nitrogen 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.

A method for solving the problem P That is, the present invention provides a functionally separated photoreceptor having a charge generation layer and a charge transport layer, in which the charge transport layer is composed of silicon atoms and germanium atoms generated from a plasma polymerization reaction. A hydrogenated or fluorinated amorphous carbon film containing at least one of the following, and the charge generation layer containing at least one of phosphorus atoms and boron atoms as well as nitrogen atoms. Regarding a photoreceptor characterized by being an amorphous silicon film (hereinafter, the charge transport layer according to the present invention is an a-C film and the charge generation layer is an a-
3i film).

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

That is, the present invention provides a hydrogenated amorphous carbon film containing at least 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 nitrogen 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, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane,
tocosan, tricosane, tetracosan, pentacosan,
Normal paraffins such as hexacosane, heptacosane, octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, etc., as well as isobutane, isopentane, neopentane, isohexane, neohexane, 2.3-dimethylbutane, 2-methylhexane, 3- Ethylpentane, 2,2-dimethylpentane, 2
, 4-dimethylpentane, 3,3-dimethylpentane,
Tributane, 2-methylhebutane, 3-methylhebutane, 2.2-dimethylhexane, 2.2.5-dimethylhexane, 2,2.3-)dimethylpentane, 2.2.4
Isoparaffins such as -trimethylpentane, 2.3°3-trimethylpentane, 2,3.4-trimethylpentane, isonanone, etc. are used. Examples of unsaturated hydrocarbons include ethylene, propylene, isobutylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl -Olefins such as 2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-nonene, 1-decene, and allene, methylalene, butadiene, pentadiene, hexadiene,
Diolefins such as cyclopentadiene, triolefins such as ocimene, allocimene, myrcene, hexatriene, acetylene, butadiyne, etc.
゜3-pentadiyne, 2.4-hexadiyne, methylacetylene, 1-butyne, 2-butyne, 1-pentyne, 1
-Hexyne, 1-heptyne, 1-octyne, 1-nonine, 1-decyne, etc. are used.

Examples of alicyclic hydrocarbons include cyclopropene, cyclobutane, cyclopentane, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloparaffins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, and cycloolefins such as limonene, tervirun, phelandrene, sylvestrene, thuene, carene, pinene, bornylene, casifene, fuenchen , cycloundecane, tricyclene, pisabolene, zingiberene, curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, campholene, phylloclatene, bodocarbrene, mirene, and other terpenes, steroids, and the like are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, pseudocumene, mesitylene, prenitene, isodurene, durene,
Pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, 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 using a conventional method for organic elemental analysis, for example, ON.
This can be determined by using H analysis.

The amount of hydrogen atoms contained in a-CM in the present invention is
It varies depending on the form of the film-forming equipment and the conditions during film-forming, but
For example, increasing the substrate temperature, decreasing the pressure, decreasing the dilution rate of the raw material hydrocarbon gas, increasing the applied power,
Measures such as lowering the frequency of the alternating electric field, increasing the strength of the DC electric field superimposed on the alternating electric field, or a combination thereof have the effect of lowering the amount of hydrogen contained.

The thickness of the a-C film as the charge transport layer in the present invention is 5 to 5
A suitable 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-CM has high light transmittance, high dark resistance, and is rich in charge transport properties.As mentioned above, even if the film thickness is 5 μm or more, carriers are transported without being trapped and contribute to bright attenuation. It is possible.

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

In the present invention, in addition to hydrocarbons, 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 silicon compounds or germanium compounds 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 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 at %, the silicon atoms, which had ensured suitable transport properties when added in small amounts, instead exhibit an effect that increases the resistance of the film, resulting in a decrease in sensitivity. It ends up. On the other hand, the amount of germanium atoms is 1
If the amount exceeds 0 atomic %, the germanium atoms, which 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, 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. By reducing the amount of compound introduced, a-
It is possible to reduce the amount of silicon atoms or i-germanium atoms added to the C film.

In the present invention, silane gas, disilane gas, or fluorinated silane gas is used to form a-Sivc. 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, a nitrogen compound gas such as nitrogen gas, ammonia gas, nitrous oxide gas, or nitrogen dioxide gas is used as a raw material gas for containing nitrogen 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 nitrogen atoms contained as a chemical modifier is 0.001 to 3 at% based on the total constituent atoms.
It is. Here, the content of nitrogen 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 nitrogen atoms in the film is lower than 0.001 at%, the electric resistance value of the a-Si film decreases, making it difficult for the a-3i film to be subjected to electric fields 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 nitrogen atoms in the film is higher than 3 at%, the electrical resistance value of the a-5i 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 nitrogen 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 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 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-5i film has a rich charge generation ability,
In general, in the laminated structure with the a-C film, which is the most characteristic feature of the present invention, generated carriers can be efficiently injected into the a-C film, contributing to suitable bright attenuation.

The process of forming the a-3i film from the raw material gas in the present invention is carried out in the same manner as the case of forming the a-C film.

In the present invention, the amount of nitrogen atoms, phosphorus atoms, or boron atoms contained as chemical modifiers is mainly determined by the amount of nitrogen 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 nitrogen compound gas, phosphine gas, or diborane gas introduced, nitrogen atoms, phosphorus atoms,
Alternatively, it is possible to increase the amount of boron atoms added,
Conversely, if the amount of nitrogen compound gas, phosphine gas, or diborane gas introduced is reduced, the amount of nitrogen atoms, phosphorus atoms, or boron atoms added to the a-Si 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 embodiment, a charge transport layer (2), a charge generation layer (3), and a charge transport layer (2) on a conductive substrate (1).
This figure shows a structure in which these are sequentially laminated.

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

FIG. 4 shows a conductive substrate (1), 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 Figure 1, the outermost surface is a-3il, which has poor moisture resistance.
lj, in many cases it is preferable to provide a surface protective layer in order to ensure practical humidity stability.

In the case of the configurations shown in FIGS. 2 and 3, since the outermost surface is a highly durable a-C film, there is no need to provide a surface protective layer. For the purpose of adjusting the consistency with respect to various elements within the copying machine, such as prevention, a surface protective layer may be provided as another form.

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

FIG. 6 shows, as a 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 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 a gas phase by discharge decomposition under reduced pressure, and diffuses active neutral species or charged species contained in the generated plasma atmosphere onto the substrate, using electric force or magnetic force. It is preferable that the material be generated by a so-called plasma polymerization reaction, in which the material is introduced by force or the like and deposited as a solid phase by a recombination reaction on the substrate.

FIG. 7 shows a photoconductor manufacturing apparatus according to the present invention, and in the figure (701) to (706) are first to sixth tanks in which the raw material compound and carrier gas, which are in a gas phase at room temperature, are sealed, respectively. The tanks are the first to sixth control valves (707)
~ (712) and the first to sixth flow rate fII controllers (713
) to (718). In the figure (719) to (
7211 First to third containers containing raw material compounds that are in a liquid or solid state at room temperature, each container can be heated by the first to third temperature controllers (722) to (724) for vaporization. Roughly speaking, each container is connected to seventh to ninth control valves (725) to (727) and seventh to ninth flow rate regulators (728) to (730). After these gases are mixed in the mixer (731), the main pipe (732)
It is sent into the reaction chamber (733) via. 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. . A ground electrode (735) and a power application electrode (736) are installed facing each other in the reaction chamber, and each electrode is heated! (737) allows for heating. A high frequency power matching device (738) is connected to the power application electrode (736).
high frequency power supply (739L low frequency power matching box (7
A low frequency power source (741) is connected through a low-frequency power source (741) and a DC power source (743) is connected through a low-pass filter (742), and power with different frequencies can be applied by a connection selection switch (744). The pressure inside the reaction chamber (733) can be adjusted by a pressure control valve (745), and the pressure inside the reaction chamber (733) can be reduced through an exhaust system selection valve (746), a diffusion pump (747), and an oil rotary valve. Pump (74
8), or by a cooling exclusion device (749), a mechanical booster pump (750), or an oil rotary pump (748). The exhaust gas is further rendered safe and harmless by an appropriate exclusion device (753) before being exhausted into the atmosphere. These exhaust system piping can also be heated by appropriately placed piping heaters (734) to prevent the vaporized gas of the raw material compound, which is in a liquid or solid phase state at room temperature, from condensing on the way. ing. Reaction chamber (7
33) can also be heated by the reaction chamber heater (751) for the same reason, and a conductive substrate (
752) can be installed. In FIG. 7, a conductive substrate (7
52) are fixedly arranged on the ground type 8!1 (735), but may be fixedly arranged on the power application fi (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 arranged inside. Conductive substrate (
852) There is also a cylindrical power application electrode (
836) is arranged, and an electrode heater (837) is arranged outside. The conductive substrate (852) is rotatable using an external drive motor (854).

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

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

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

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

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

Charge transport layer forming step: In the glow discharge decomposition apparatus shown in FIG. Control valve (7
10), hydrogen gas is released from the first tank (701),
Germanic gas was flowed from the fourth tank (704) into the first and fourth flow rate controllers (713 and 716) under an output pressure of 1.0 Kg/cm2. At the same time, the first
Myrcene gas is transferred from the container (719) to the first temperature controller (722).
) was made to flow into the seventh flow rate controller (728) at a temperature of 70°C. Using each flow controller, adjust the flow rate of hydrogen gas to 20
The flow rate of 5CCm% germane gas was set to 5 sec, and the flow rate of myrcene gas was set to 5 sec, and the gas flowed into the reaction chamber (733) from the main pipe (732) via an intermediate mixer (731). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 1.5 Torr. On the other hand, as the conductive substrate (752), use an aluminum substrate of 50 fir x 50 mm x 3 mm thickness, heat it to 150°C in advance, and when the gas flow rate and pressure are stable, set the connection selection switch ( 744) connected to the low frequency power supply (744).
41) and applied 110W 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 500 KHz at a frequency of 500 KHz, and the conductive substrate (75
2) An a-C film having a thickness of 15 μm was formed thereon as a charge transport layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Organic elemental analysis of the a-C film obtained as described above revealed that the amount of hydrogen atoms contained was 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 control valve (707L), the fifth control valve (711L) and the sixth control valve (712) are opened, and the first tank (701L) is opened.
) from hydrogen gas, nitrogen gas from the fifth tank (705),
and silane gas from the sixth tank (706) at an output pressure of I
The first, fifth and fifth SIf were flowed into the quantity controllers (713, 717 and 718) under Kg/am2. At the same time, the fourth control valve (710) is released and the fourth tank (710) is released.
04) Diborane gas diluted to 1100pp with hydrogen gas is subjected to the fourth flow rate control under an output pressure of 1.5Kg/cm2! (716). Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec, the nitrogen gas flow rate to 10105e, and the silane gas flow rate to 100 s.
The flow rate of diborane gas diluted to 1100 pp with CCm% hydrogen gas was set to 1105 CC, and the reaction chamber (73
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 with the gas flow rate and pressure stable, it is heated at a frequency of 13°56MHz from a high frequency power source (739). A power of 40 Watts was applied to the power application electrode (736) to generate glow discharge. This discharge was performed for 5 minutes, and the thickness was 0.
．． A charge generation layer of 3 μm was obtained.

The obtained a-5iHR was subjected to in-metal ONH analysis (N-field produced fracture EMGA-1300), Auger analysis, and IMA analysis, and it was found that the hydrogen atoms contained were 24 at% and boron Atom is 10 atoms pp
m, nitrogen atoms were 1.0 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 -580V (+720V), 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 38 .mu./.mu.m (47 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 25 seconds (approximately 32
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, and the amount of light required was 4.2 lux · seconds (1.8 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 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 made into a cavity vacuum of about 10-6 Torr, and then the first control valve (707) and the second 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), respectively, at an output pressure of 1. 1st and 2nd under OKg/am2
, and the sixth flow rate controller (713, 714, and 718)
It flowed inside. Using each flow rate controller, set the flow rate of hydrogen gas to 60 scm, and the flow rate of butadiene gas to 60 scc.
m, and the flow rate of silane gas is set to 5 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 fir x 50 x 3 mm thick, heat it to 250°C in advance, and when the gas flow rate and pressure are stable, set the connection selection switch ( The low-frequency power source (741) connected to the conductive substrate (744) is turned on, and 120 Watt power is applied to the power application electrode (736) at a frequency of 400 KHz to perform a plasma polymerization reaction for about 40 minutes. 752) A 15 μm thick a-C film was formed thereon as a charge transport layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

When 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. Also,
According to Auger analysis, the amount of silane atoms contained was 5.2 at % based on the total constituent atoms.

Charge generation layer forming step: Next, the first control valve (707) and the fifth control valve (711L
and the sixth control valve (712), and the first tank (70
1), hydrogen gas from the fifth tank (705), ammonia gas from the sixth tank (706), and silane gas from the sixth tank (706).
It was flowed into the first, fifth and sixth flow controllers (713, 717 and 718) under an output pressure of I K g/0 m2. At the same time, the fourth control valve (710) is opened, and diborane gas diluted to toppm 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, ammonia gas flow rate 2sec, silane gas flow rate 101005e, 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 0.9 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.
Power application electrode (73,6) under Hz! , :45Wa
A power of t t was applied to generate a glow discharge. This discharge was carried out for 5 minutes to obtain a charge generation layer having a thickness of 0.3 μm. - ONH analysis in metal for the obtained a-5f film (EMGA-1300 manufactured by Itaba Seisakusho)
, Auger analysis, and IMA analysis showed that hydrogen atoms that could be contained were 21 at %, boron atoms were 11 at pI) m%, and nitrogen atoms were 0.3 at % based on the total constituent atoms.

Characteristics: When the obtained photoreceptor was used with both negative and positive charging in a conventional Carlson process, the following performance was obtained. Here, the measured values during positive charging are shown in parentheses, and the highest charging potential is -860V (+940V), 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 56 V/.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 34 seconds (approximately 37 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. Furthermore, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential, and the amount of light required was 2.9 lux · seconds (1.8 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 device shown in FIG. 7, first, the inside of the reaction device (733) is made into a high vacuum of about 10-6 Torr, and then the first control valve (707) and the second control valve (708
) 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) to an output pressure of 1. 1st and 2nd under 0Kg;'cm2
, and 6th stream M control number device (713, 714, and 718)
It flowed inside. Using each flow rate controller, the flow rate of hydrogen gas was set to 60 sec, and the flow rate of ethylene gas was set to 6°5 cc.
Set the flow rate of rn % and silane gas to 3 seconds and mix in the middle! (731) through the main pipe (7
32) into the reaction chamber (733). After each flow rate stabilized, the pressure inside the reaction chamber (733) reached 1.8T.
The pressure control valve (745) was adjusted so that the

On the other hand, as the conductive substrate (752),! 50X horizontal 50
× Using an aluminum substrate with a thickness of 3 mm, heat the temperature at 250°C in advance.
After heating to , and with the gas flow and pressure stable,
Turn on the high frequency power supply (739) connected in advance by the connection selection switch (744), and turn on the power application type tIi (7
36) 180Watt power to frequency 13.56MH
A plasma polymerization reaction was carried out for about 10 hours by applying voltage under z, and a 15 μm thick a-CM 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 45 at % based on the total amount of carbon atoms and hydrogen atoms. Further, according to Auger analysis, the amount of silicon atoms that could be contained was 0.4 at % based on the total constituent atoms.

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)
! hydrogen gas from the third tank (701), tetrafluorosilane gas from the third tank (703), nitrogen gas from the fifth tank (705), and the sixth tank (706).
) under an output pressure of IKg/cm2.
, third, fifth, and sixth flow rate controllers (713, 715,
717 and 718). At the same time, the fourth control valve (710)! Release, 4th Tan'y (704)
Diborane gas diluted to 1100 pp with hydrogen gas was passed through the fourth flow controller (
716) Inflow began to flow inside. Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sec, the tetrafluorosilane gas flow rate to 50 sec, and the nitrogen gas flow rate to 1 sec.
, the flow rate of silane gas was 50 sec, and the flow rate of hydrogen gas was 110 sec.
The flow rate of diborane gas diluted to 0pp is 101005
e 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, 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 type i (736)
A power of 35 Watts 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-St film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 22 at.% of the total constituent atoms, and the boron atoms were 95 at.ppm.
, 5 at% of fluorine atoms, and 0.1 at% of nitrogen 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 -740V (+710V), that is,
Since the total photoreceptor film thickness was 15.degree. 3 .mu.m, the charging ability per 1 .mu.m was extremely high at 48 V/.mu.m (46 V/.mu.m), and from this it was understood that the photoreceptor had sufficient charging performance.

“Also, the time required for II# to decay from Vmax to 90% of Vmax in the dark is approximately 15 seconds (
(approximately 16 seconds), and from this it was understood that the battery 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, and the required amount of light was 2.0.
lux-second (1, flux-second), and from this it was understood that it has sufficient photosensitivity performance.

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

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

X Execution 4 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 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. The first, second, and sixth flow rate controllers (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 flow rate of germane gas to 9sc.
cm, and flowed into the reaction chamber (733) from the main pipe (732) via the mixing lid (731) midway. After each flow rate is stabilized, the pressure regulating valve (745) is adjusted so that the pressure in the reaction chamber (733) becomes 2.0 Torr.
) was adjusted. 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 heated to 190°C in advance, and with the gas flow rate and pressure stable, a high-frequency power source ( 739) and applied a power of 90 Watts to the power application electrode (736) at a frequency of 13.
A plasma polymerization reaction was performed for about 3 hours and 20 minutes by applying a frequency of 56 MHz, and a 15 μm thick film was formed on the conductive substrate (752).
The a-C film was formed as a charge transport layer. After completing the film formation, stop applying power, close the control valve, and open the reaction chamber (733).
The inside was thoroughly 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. 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, the first control valve (707) and the fifth control valve (711)
, and the sixth control valve (712), and the first tank (7
01), nitrogen gas from the fifth tank (705), and silane gas from the sixth tank (706) at the first, fifth, and sixth flow rate controls under an output pressure of IKg/cm2.
It was made to flow into JW (713, 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 seconds and the nitrogen gas flow rate to 0. Olsecm.

Increase the flow rate of silane gas to 1001005e and 110% with hydrogen gas.
The flow rate of diborane gas diluted to 0pp is 10105e.
was set so that it would flow 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.
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. A power of 35 Watts was applied to the power application electrode (736) to generate glow discharge. This discharge was carried out for 59 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 25 at% of the total constituent atoms, and the boron atoms were 10 at pI'
The ms nitrogen atom was 0.001 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 -840V (+865V), 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 55 V/.mu.m (57 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 40 seconds (approximately 38
seconds), and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential.The amount of light required was 4.5 lux seconds (4.4 lux・seconds), and from this it was understood that it had 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.

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. 2 control valves (7
08) 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/am2,
Second and sixth flow controllers (713, 714, and 71
8) It was allowed to flow into the interior. Using each flow rate controller, set the flow rate of hydrogen gas to 60 seconds and the flow rate of butadiene gas to 60 seconds.
ecm and the flow rate of silane gas are set to 10105e, and the main pipe (
732) into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 2.0.
The pressure control valve (745) was adjusted so that the pressure was Torr. On the other hand, as a conductive substrate (752),
130 mm in advance using an aluminum substrate with a thickness of 3 mm.
℃, 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), and connect the power application electrode (73).
6), a plasma polymerization reaction was carried out for about 30 minutes by applying a power of 180 Watts at a frequency of 100 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 muscle adjustment 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, the first control valve (707) and the fifth control valve (711L
and the sixth control valve (712), and the first tank (70
Hydrogen gas from 1), nitrogen 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) 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 (70
4) Phosphine gas diluted to 10 ppm with hydrogen gas 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 nitrogen gas flow rate to 3 sec cm%, and the silane gas flow rate to 20 sec.
Set the flow rate of phosphine gas diluted to 1100 pp with hydrogen gas to 10105e,
33). 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 is formed is heated to 250°C, and with the gas flow rate and pressure stable, it is heated at a frequency of 13°56MHz 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-St film was subjected to ONH analysis in metal (EMGA-1300 manufactured by Itaba Seisakusho), Auger analysis, and I
When MA analysis was performed, the hydrogen atoms contained were 18 at %, the phosphorus atoms were 12 at ppm,
The nitrogen 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 -800V (+950V), 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 52 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 38 seconds (approximately 42 seconds).
seconds), and from this it was understood that it had sufficient charge retention performance. Furthermore, after initial charging to the highest charging potential, white light was used to brightly attenuate the surface potential to 20% of the highest charging potential, and the required amount of light was 2.6 lux · seconds (9.2 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. Figure 1 Figure 2 Figure 4 Figure 6 Procedural amendment dated October 21, 1986

Claims (1)

[Claims] In a functionally separated photoreceptor having a charge generation layer and a charge transport layer, the charge transport layer is a hydrogenated amorphous carbon film containing at least one of silicon atoms and germanium atoms, and the charge generation layer is a hydrogenated amorphous silicon film containing nitrogen atoms and at least one of phosphorus atoms and boron atoms, or a fluorinated amorphous silicon film containing nitrogen atoms and at least one of phosphorus atoms and boron atoms. A photoreceptor characterized by being an amorphous silicon film.