JPS62220960A - Photosensitive body - Google Patents

Abstract

PURPOSE:To enhance electrostatic charge transfer performance and potential acceptance, to obtain sufficient surface potential, and a good image by using a photosensitive body composed of at least a charge generating layer, and a charge transfer layer of a specified hydrocarbon polymer film. CONSTITUTION:The functionally separated photosensitive body is provided with the charge generating layer 3 and the charge transfer layer 2, and the hydrocarbon plasma-polymerized film having, in its infrared adsorption spectra, and absorption coefficient alpha1 due to a methyl group -CH3 at the peak near 2,960cm<-1> and that alpha2 at the peak near 2,925cm<-1> due to a methylene group -CH2-, and an alpha1/alpha2 ratio of 0.5-1.5, preferably, 0.7-1.3, especially, 0.8-1.2, thus permitting the photosensitive body using this plasma-polymerized film as the charge transfer layer to be superior in charge transfer performance and acceptance potential, and to obtain a good image and a thin photosensitive body in the case of using a-Si for the charge generating layer.

Description

[Detailed description of the invention] Industrial applications The present invention relates to photoreceptors, particularly electrophotographic photoreceptors.

Prior art Invention of the Carlson method (1938, tlsP22217
6) Since then, the field of application of electrophotography has continued to make remarkable progress, and various materials have been developed and put into practical use as photoreceptors for electrophotography.

The main electrophotographic photoreceptor materials conventionally used include inorganic substances such as amorphous selenium, selenium arsenide, selenium telluride, cadmium sulfide, zinc oxide, amorphous silicon, polyvinyl carbazole, metal phthalocyanine,
Examples include organic substances such as disazo pigments, trisazo pigments, perylene pigments, triphenylmethane compounds, triphenylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, oxazole compounds, and oxadiazole compounds.

In addition, the configurations include a single-layer structure in which these substances are used alone, and a bang-like structure in which these substances are dispersed in a binder.
Examples include a mold structure and a laminated structure in which a charge generation layer and a charge transport layer are provided for each function.

However, the conventionally used electrophotographic photoreceptor materials each have drawbacks.

One of these is their toxicity to the human body, and all inorganic substances, except for the amorphous silicon mentioned above, have unfavorable properties.

In addition, in order for an electrophotographic photoreceptor to be actually used in a copying machine, it must always maintain stable performance f( However, the organic substances mentioned above have poor durability and many unstable factors in terms of performance.

In order to solve these problems, in recent years, plasma chemical vapor deposition (hereinafter referred to as plasma chemical vapor deposition) has been applied to photoreceptors, especially electrophotographic photoreceptors.
Amorphous silicon (hereinafter abbreviated as a-Si) manufactured by VD (VD method) has come to be used.

The a-Si photoreceptor has various excellent properties. However, since a-5t has a large dielectric constant ε of about 12, there is a problem in that a film thickness of at least about 25 μm is essentially required in order to obtain a sufficient surface potential as a photoreceptor. a
In the plasma CVD method, the -Si photoreceptor requires a long time to produce because the film deposition rate is slow, and the longer the production time becomes, the more difficult it becomes to obtain a homogeneous film of a-Si. As a result, the a-Si photoreceptor has drawbacks such as a high probability of image defects such as white spot noise and high raw material costs.

Although various attempts have been made to improve the above drawbacks, it is essentially not desirable to make the film thinner than this.

On the other hand, the a-Si photoreceptor also has drawbacks such as poor adhesion between the substrate and the a-8t, as well as poor corona resistance, environmental resistance, and chemical resistance.

In order to solve such problems, it has been proposed to provide an organic plasma polymerized film as an overcoat layer or undercoat layer of an a-Si photoreceptor. Examples of the former are, for example, JP-A-60-61761 and JP-A-59.
JP-A-214859, JP-A-51-46130, JP-A-50-20728, etc. are known, and examples of the latter include JP-A-60-63541.
No. 59-136742, JP-A-59-136742, JP-A-59-136742
-38753, JP-A-59-2'a161, JP-A-56-60447, etc. are known.

Organic plasma polymerized films can be prepared from all kinds of organic compound gases such as ethylene gas, benzene, and aromatic silanes (e.g., Ni, T, Be1l).
), M., Shen et al., Journal of Applied Polymer Science (Jou
nal orApplied Polymer 5
science), Vol. 17, pp. 885-892 (197
3), etc.), but organic plasma polymerized films produced by conventional methods are used only for applications that require insulation. Therefore, these films were considered to be insulating films having an electrical resistance on the order of lo'' ΩGM, like ordinary polyethylene films, or at least were used with the understanding that they were such films.

The technique described in Japanese Patent Application Laid-Open No. 60-61761 discloses a photoreceptor coated with a diamond-like carbon insulating film having a thickness of 500 to 2 μm as a surface protective layer.

This carbon thin film is used to improve the corona discharge resistance and mechanical strength of the a-Si photoreceptor. The polymer membrane is very thin, and charges move through the membrane through the tunnel effect, so the membrane itself does not require charge transport ability. Furthermore, there is no mention of the carrier transport properties of organic plasma polymerized films, and a
- It does not solve the above-mentioned essential problem of Si.

Japanese Unexamined Patent Publication No. 59-214859 discloses a technique of coating an organic transparent film with a thickness of about 5 μm as an overcoat layer by plasma polymerization of organic hydrocarbon monomers such as ethylene and acetylene. This improves the peeling, durability, vinyl pole, and production efficiency of a-Si photoreceptors. There is no description whatsoever regarding the carrier transport properties of organic plasma polymerized films, and it does not solve the above-mentioned essential problems of a-Si.

JP-A No. 51-46130 discloses that N-vinylcarbazole is coated on the surface with a thickness of 3 μm to 0.0 μm by glow discharge.
A photoreceptor on which an organic plasma polymerized film of 0.01 μm is formed is disclosed. The purpose of this technology is to make it possible to use a poly-N-vinylcarbazole photoreceptor, which could only be used with positive charging, with bipolar charging. This membrane is o, oot
It is very thin at ~3 μm and is used as an overcoat.

It is thought that the polymeric membrane is very thin and does not require charge transport ability. Furthermore, there is no description whatsoever regarding the carrier transportability of the polymeric membrane, and it does not solve the above-mentioned essential problems of a-9i.

JP-A No. 50-20728 discloses a sensitizing layer on a substrate,
A technique has been disclosed in which an organic photoconductive electrical insulator is sequentially laminated and a glow discharge polymerized film with a thickness of 0.1 to 1 μm is formed thereon. It is used as an overcoat to protect the skin.

Polymerized membranes are very thin and do not require charge transport capabilities.

Furthermore, there is no description whatsoever regarding the carrier transport properties of the polymeric membrane, and it does not solve the above-mentioned essential problems of a-Si.

JP-A-60-6.3541 discloses a photoreceptor using a diamond-like organic plasma polymerized film of 200 to 2 μm as the undercoat layer of a-5i, but the organic plasma polymerized film is The purpose is to improve the adhesion between a-Si and a-Si.

Polymerized membranes can be very thin, charges move through the membrane by tunneling, and the membrane itself does not require charge transport capabilities. Furthermore, there is no description whatsoever regarding the carrier transport properties of the organic plasma polymerized film, and it does not solve the above-mentioned essential problems of a-Si.

JP-A-59-28161 discloses a photoreceptor in which an organic plasma polymerized film and an a-Si are sequentially formed on a substrate. The organic plasma polymerized film is an undercoat layer that takes advantage of its insulating properties and functions as a blocking layer, adhesive layer, or peel prevention layer. Polymerized membranes can be very thin, charges move through the membrane by tunneling, and the membrane itself does not require charge transport capabilities. In addition, there is no description whatsoever regarding the carrier transport properties of the organic plasma polymerized film, and it does not solve the above-mentioned essential problems of a-9i.

JP-A No. 59-38753 discloses that 10 to 100
Form an organic plasma-polymerized thin film on which a-S
A technique for forming an i-layer is disclosed. The organic plasma polymerized film is an undercoat layer that takes advantage of its insulating properties, and functions as a blocking layer or a peel-preventing layer. Polymerized membranes can be very thin, charges move through the membrane by tunneling, and the membrane itself does not require charge transport capabilities. Furthermore, there is no description whatsoever regarding the carrier transport properties of the organic plasma polymerized film, and it does not solve the above-mentioned essential problems of a-Si.

Japanese Patent Application Laid-open No. 59-136742 discloses that about 5μ
A semiconductor device is disclosed in which an organic plasma polymerized film and a silicon film of m are sequentially formed. However, although the purpose of this organic plasma polymerized film is to prevent the diffusion of aluminum, which is the substrate, into the a-9t, there is no description of its manufacturing method, film quality, etc. Furthermore, there is no description whatsoever regarding the carrier transport properties of organic plasma polymerized films, and a-8
It does not solve the above-mentioned wooden problem of i.

JP-A-56-60447 discloses a method for forming an organic photoconductive film by plasma polymerization, but there is no mention of the possibility of application in electrophotography, and furthermore, there is no mention of the possibility of application in electrophotography. Alternatively, it is disclosed as a photoconductive layer, which is different from the present invention. Moreover, it does not solve the above-mentioned woody problems of a-9i.

Problems to be Solved by the Invention As mentioned above, organic polymer films conventionally used in photoreceptors have been used as undercoat layers or overcoat layers, but these do not require a carrier transport function. It is a film, and it is used based on the judgment that the organic polymer film is insulating. Therefore, its thickness is at most 5μ
It is used only as an extremely thin film, about the size of a skin, and the carriers pass through the film through the tunnel effect, or if a tunnel effect cannot be expected, the film is thin enough that there is no problem with the residual potential in practical use. It is only used in

While considering the application of organic polymer films to photoreceptors, we found that organic polymer films, which were originally thought to be insulating, decreased electrical resistance by increasing the content of methyl groups. It was discovered that the material began to exhibit charge transport properties.

By utilizing this new knowledge, the present invention solves all the problems of the conventional a-9i photoreceptor, such as problems in the a-Si film thickness, manufacturing time, manufacturing cost, etc. It is an object of the present invention to provide a photoreceptor using an organic polymer film, particularly an organic plasma polymer film, which has a completely different purpose and characteristics from the above, and a method for manufacturing the same.

Means for solving the problem, that is, the present invention provides a charge generation layer (3) and a charge transport layer (2).
) in a functionally separated photoreceptor having a charge transport layer (
As 2), a hydrocarbon plasma polymerized film is provided, and the infrared absorption spectrum of the polymerized film is determined by methyl (-CH*) groups.
The peak absorption coefficient α near 960 cm-' and methylene (
-cI-r, -) group's peak absorption coefficient α near 2925 cm-', and the ratio αl/α.

0.5 to 1.5.

The photoreceptor of the present invention is composed of at least a charge generation layer and a charge transport layer.

The photoreceptor of the present invention is characterized by having a hydrocarbon polymer film as a charge transport layer, and furthermore, the methyl groups and methylene groups formed in the polymer film have two methyl groups in the infrared absorption spectrum.
The ratio α, /α, between the peak absorption coefficient α1 near 960 ci-′ and the peak absorption coefficient α near 2925 cm-′ due to the methylene group is 0.5 to 1.5 (
Hereinafter, the polymer film of the present invention will be referred to as a-C@).

The absorption coefficient of the infrared absorption spectrum in the present invention is determined from the transmittance and film thickness using the following formula [1] [where α is the absorption coefficient, d is the film thickness, and 'r/'ro represents the transmittance. ] It is expressed as .

The a-C film of the present invention has an infrared absorption spectrum with a peak absorption coefficient α1 around 2960 cm-' due to methyl groups, a peak absorption coefficient α1 around 2925 cm-' due to methylene groups,
The ratio of 0.5 to 1.5, more preferably 0.7 to 1.5
1.3, especially suitable when 0.8 to 1.2, and 0
．． If it is less than 5, suitable transport properties cannot be obtained and it cannot be used as an electrophotographic photoreceptor, and if it is larger than 1.5, the charging ability is decreased, the film quality is deteriorated, and the film formability is decreased.

In general, the peak absorption coefficient derived from methyl and methylene groups follows formula [I], and only when the value of α, /α, is larger than 0°5 does the specific resistance become approximately 1011 Ωcm or less, and the carrier mobility becomes IO''"'cm" (V・5ec
) or more.

The a-C film of the present invention contains various groups derived from carbon atoms, such as methyl groups, methylene groups, or methine groups, or carbon atoms with various bonding modes, such as single bonds, double bonds, triple bonds, etc. exists, but according to formula [I] α
In the present invention, it is important that the value of 1/α is 0.5 to 1.5.

The thickness of the a-0 layer is suitably 5 to 50 .mu.m, particularly 7 to 20 .mu.m; if it is thinner than 5 .mu.m, the surface potential is low and sufficient density of the copied image cannot be obtained. If it is thicker than 50 μm, it is not preferable in terms of productivity. This a-0 layer has excellent light transmittance, relatively high dark resistance, and is rich in charge transport properties, and does not cause charge traps (transports carriers) even when the film thickness is 5 μm or more as described above.

Hydrocarbons are used as the organic gas for forming the a-0 layer.

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

Examples of the hydrocarbons used include methane series hydrocarbons, ethylene series hydrocarbons, acetylene series hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

Examples of methane series hydrocarbons include methane, ethane,
Propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane,
Normal paraffins such as heptadecane, octadecane, nonadecane, eicosane, heneicosane, tocosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octadecane, nonacosane, triacontane, dotriaconcune, pentatriaconcune, isobutane, isopentane, neopentane, isohexane, Neohexane, 2゜3-dimethylbutane,
2-Methylhexane, 3-ethylbenkune, 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-)dimethylpentane, 2.3゜3
Isoparaffins such as -trimethylpentane, 2,3,4-trimethylpentane, isonanone, etc. are used.

Examples of ethylene series hydrocarbons include ethylene, propylene, isobutylene, 1-butene, 2-butene, l-
Pentene, 2-pentene, 2-methyl-1-butene, 3
-Methyl-1-butene, 2-methyl-2-butene, 1-
hexene, tetramethylethylene, 1-heptene, l-
Olefins such as octene, l-nonene, l-decene, diolefins such as allene, methylalene, butadiene, pentadiene, hexadiene, cyclopentadiene, and triolefins such as ocimene, allocimene, myrcene, hexatriene, etc. are used.

Examples of acetylenic hydrocarbons include acetylene,
Methylallenene, l-butyne, 2-nonane, 1-pentyne, l-hexyne, 1-heptyne, l-octyne, l
-nonine, l-decyne, etc. are used.

Examples of alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopencune, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, and the like. and cycloolefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, limonene, tervirun, phelandrene, sylvestrene, thuene, carene, pinene, bornidine, kanghuen, fuenchen, Terpenes such as cycloundecane, tricyclene, bisabodin, zingibedine, curcumene, humulene, cadinensesquivenichen, selinene, caryophyllene, naphthalene, cedrene, canhodine, phylloclatene, bodocarbrene, midine, 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.

Suitable carrier gases include H2, Ar, Ne5He, and the like.

In the present invention, it is most preferable to form the a-C organic polymer film through a plasma state such as a direct current, high frequency, or microwave plasma method, but it may also be formed through an ion state such as ionization vapor deposition or ion beam vapor deposition. Alternatively, it may be formed from neutral particles using a vacuum evaporation method, a sputtering method, or a combination thereof.

What is important in this case is to form the organic polymer film so that the infrared absorption peak ratio αl/α based on methyl groups and methylene groups is 0.5 to 1.5 as described above.

Further, it is preferable that the charge generation layer is formed by the same method as the a-C film, as this leads to reductions in manufacturing equipment costs and process labor.

The charge generation layer of the photoreceptor of the present invention is not particularly limited, and may be made of amorphous silicon (a-Si)@(in order to change the characteristics, various different elements such as H, C10, S, N, P, B,
may contain halogen, Ge, etc., and may have a multilayer structure), Se film, 5e-As film, Se-T
e film, CdS film, copper phthalocyanine, inorganic substances such as zinc oxide and/or bisazo pigments, triarylmethane dyes, chian dyes, oxazine dyes, xanthine dyes, soanine dyes, styryl dyes, pyrylium dyes Resins containing organic substances such as dyes, azo pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, induthrone pigments, squarylium pigments, and phthalonanine pigments. Examples include membranes and the like.

In addition, any material that absorbs light and generates charge carriers with extremely high efficiency can be used.

The charge generation layer may be provided at any position on the photoreceptor, for example, the top layer, bottom layer, or intermediate layer. The film thickness depends on the type of material, especially its spectral absorption characteristics, exposure light source, purpose, etc., but generally it is 90% for 550 nm light.
The setting is made so that the above amount of absorption can be obtained. In the case of a-St, it is 0.1 to 3 μm.

In the present invention, a heteroatom other than carbon or hydrogen may be mixed in order to adjust the charging characteristics of the a-Cm charge transport layer. For example, in order to further improve the hole transport properties, a different atom from No. 1 of the periodic table or a halogen atom may be mixed. In order to further improve the electron transport properties, a group V different atom of the periodic table or an alkali metal atom may be mixed. In order to further improve the transport characteristics of both positive and negative carriers, Si, Ge, alkaline earth metal, or chalcogen atoms may be mixed. A plurality of these atoms may be used, or they may be mixed only at specific positions in the charge transport layer depending on the purpose, or they may have a concentration distribution, etc., but in any case, the important thing is that , the ratio αI/α of infrared absorption peaks based on methyl groups and methylene groups in the polymer film
2 is 0.5 to 1.5 as described above.

1 to 12 are schematic cross-sectional views showing one embodiment of the photoreceptor of the present invention. In the figure, (1) indicates the substrate, (2) the a-C film as a charge transport layer, and (3) the charge generation layer. In the photoreceptor of the embodiment shown in FIG. 1, when the photoreceptor is charged, for example, ten times and then imaged, charge carriers are generated in the charge generation layer (3) and electrons neutralize the surface charges. On the other hand, holes are transported to the substrate (1) side, guaranteed by the excellent charge transport properties of a-CM (2). When the photoreceptor shown in FIG. 1 is used with one charge, electrons are transported through the a-C film (2) in the opposite manner to the above.

The photoreceptor shown in Fig. 2 is an example in which an a-C film (2) is used as the uppermost layer. Holes are transported through the C film (2).

The photoreceptor shown in FIG. 3 is an example in which a-C1li (2) is used above and below the charge generation layer (3), and when used with ten charges,
Electrons pass through the upper a-G film (2) and the lower a-C film (
2) Holes are transported through the upper a-C film (2), and when used with - charging, the holes are transported through the upper a-C film (2) and the lower a-C film (2).
Electrons are transported inside.

The photoreceptors shown in FIGS. 4 to 6 are examples of the photoreceptors shown in FIGS. 1 to 3 in which a surface protective layer with a thickness of 0.01 to 5 μm is further provided as an overcoat layer (4).
This is intended to protect the charge generation layer (3) or the charge transport layer a-C film (2) and improve the initial surface potential depending on the system and environment in which the photoreceptor is used. The surface protective layer may be formed of any known material, and in the present invention, it is desirable to provide it by organic plasma polymerization from the viewpoint of the manufacturing process. The a-C membranes of the present invention may also be used. This protective layer (4) may also contain upward heteroatoms if necessary.

The photoreceptors shown in FIGS. 7 to 9 are examples of the photoreceptors shown in FIGS. 1 to 3 in which an adhesive layer or barrier layer with a thickness of 0.01 to 5 μm is further provided as an undercoat layer (5). , the adhesion or injection prevention effect is aimed at depending on the substrate (1) used or its processing method.

The undercoat layer may be made of a known material, and in this case as well, it is desirable to provide it by organic plasma polymerization.

An a-C film according to the invention may also be used. Furthermore, the photoreceptor shown in FIGS. 7 to 9 is coated with an overcoat layer (4) shown in FIGS. 4 to 6.
) may be provided (Figures 1O to 12).

The photoreceptor of the present invention has a charge generation layer and a charge transport layer. Therefore, at least two steps are required to manufacture it. When using, for example, an a-Si layer formed using a glow discharge decomposition device as the charge generation layer, it is possible to perform plasma polymerization using the same vacuum device,
Therefore, it is particularly preferable to form the a-C charge transport layer, the surface protective layer, the barrier layer, etc. by plasma polymerization.

The charge transport layer of the electrophotographic photoreceptor according to the present invention includes, for example,
Molecules in the gas phase are decomposed by discharge under reduced pressure, and activated neutral species or charged species contained in the generated plasma atmosphere are diffused onto the substrate, induced by electric force, magnetic force, etc., and regenerated on the substrate. It is preferably produced from a so-called plasma polymerization reaction, in which it is deposited as a solid phase by a bonding reaction.

FIGS. 13 and 14 show a capacitively coupled plasma CVD apparatus which is a photoreceptor manufacturing apparatus according to the present invention. FIG. 13 shows a parallel plate plasma CVD apparatus, and FIG. 14 shows a cylindrical plasma CVD apparatus.

First, explanation will be given using FIG. 13.

In FIG. 13, (701) to (706) are the first to sixth tanks in which the raw material compound and carrier gas, which are in a gas phase at room temperature, are sealed, and each tank is connected to the first to sixth control valves (707). ~ (712) and the first to sixth flow rate controllers (
713) to (71g).

In the figure, (719) to (721) are first to third containers filled with raw material compounds that are in a liquid or solid phase at room temperature, and each container has a first to third heating IK (
722) to (724), and each container has seventh to ninth control valves (725) to (727).
and seventh to ninth flow rate controllers (72111) to (730)
It is connected to the.

These gases are mixed in a mixer (731) and then sent into a reaction chamber (733) via a main pipe (732).

The pipes along the way 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. .

Inside the reaction chamber, there is a ground electrode (735) and a power application electrode (73).
6) are installed facing each other, and each electrode is connected to an electrode heater (7).
37) allows for heating.

The power application electrode is connected to a high frequency power source (739) and a low frequency power matching device (74) via a high frequency power matching device (73g).
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 can be adjusted by a pressure control valve (745), and the pressure inside the reaction chamber can be reduced by using a diffusion pump (747) and an oil rotary pump (748) through an exhaust system selection valve (746).
), or by a cooling exclusion device (749), mechanical booster pump (750), or oil rotary pump.

The exhaust gas is further rendered safe and harmless by an appropriate exclusion device (753) before being exhausted into the atmosphere.

These exhaust system pipings are also heated by appropriately placed piping heaters to prevent the vaporized gas from the raw material compounds, which are in a liquid or solid phase at room temperature, from condensing on the way.
It is said that heating is possible.

For the same reason as the reaction chamber, it is possible to heat the reaction chamber by heating 1K (751), and a conductive substrate (752) is installed on the electrode arranged inside the reaction chamber.

In FIG. 13, the conductive substrate (752) is the ground electrode (752).
35), but the power application electrode (73
B) may be fixedly arranged, or may be further arranged on both sides.

The apparatus shown in FIG. 14 is basically the same as the apparatus shown in FIG. 13, and the shape of the inside of the reaction chamber (733) is
52) is changed in accordance with the fact that it is cylindrical. The substrate also serves as a ground electrode (735), and both the power application electrode (736) and electrode heater (737) have a cylindrical shape.

In the above configuration, the reaction chamber includes a diffusion pump (747)
Reduce the pressure in advance to about 10-4 to 10-F' by
Check the degree of vacuum and desorb the gas adsorbed inside the device.

At the same time, the electrode heater (737) heats the electrode (736) and the conductive substrate (752) fixedly disposed on the electrode to a predetermined temperature.

Next, the raw material gas is transferred from the first to sixth tanks (701) to (706) and the first to third containers (719) to (721) to the first to ninth flow rate controllers (713) to (718),
(728) to (730) to introduce it into the reaction chamber (733) at a constant flow rate, and then use the pressure control valve to introduce it into the reaction chamber (733).
3) Maintain a constant reduced pressure inside.

After the gas flow rate has stabilized, press the connection selection switch (744)
For example, a high frequency power source (739) is selected, and high frequency power is applied to the power application electrode (736).

A discharge starts between both electrodes, and as time passes, the substrate (752
) a solid-phase a-C film is formed on the top.

This charge transport layer is the above-mentioned α, /α produced by the present invention.
, the ratio is 0.5 to 1.5. This α
The I/α ratio can be controlled by manufacturing conditions such as electric power, power frequency, electrode spacing, pressure, substrate temperature, source gas, gas concentration, gas flow rate, etc. For example, by increasing the power, the number of methyl groups can be reduced and the value of α, /α, ratio can be reduced. Similar control can be achieved by narrowing the electrode spacing, increasing the substrate temperature, increasing the pressure, lowering the molecular claw of the source gas, increasing the gas flow rate, etc. Further, similar control is possible even if a bias voltage of 50V-IKV is superimposed and applied from the DC power supply (743). Of course, the opposite effect can be obtained by reversing the direction of control. These control methods include multiple methods for the purpose of imparting additional properties, such as hardness and translucency, to the charge transport layer, or for the purpose of ensuring manufacturing stability.
It may be adopted as appropriate.

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

Example 1 (1) (Formation of a-0 layer) In the glow discharge decomposition apparatus shown in FIG. 2 regulating valves (707) and (7
0g/cm), CIH gas is supplied from the first tank (701), and H gas is supplied from the second tank (702) to the mass flow controller (713) under the output pressure gauge IKg/cm".
) and (714). Then, the scales of each mass flow controller were adjusted, and the flow rates of CtHh and Ha were set to 30 sec and 40 sec, respectively, and flowed into the reaction chamber (733). After each flow rate stabilizes, the internal pressure of the reaction chamber (723) becomes 0 and 5 Torr.
It was adjusted to be r. On the other hand, a conductive substrate (752)
For example, preheat to 250°C using 3X50Xb, and when the flow rate of each gas is stable and the internal pressure is stable, turn on the high frequency power supply (739) and apply 1 OOwatts of power to the power application electrode (736). Plasma polymerization was performed for about 4 hours by applying a frequency of 13.56 MI [z) to form a charge transport layer with a thickness of about 7 μm on the conductive substrate (752).

FIG. 15 shows a spectrum chart obtained by measuring a-C@ obtained as described above with a Fourier transform infrared absorption spectrometer (manufactured by Perkin-Nilmer). In Figure 15, a is 2
925 cm-', b is the transmittance peak at 2960 cm-'. The measurement was performed by placing the a-C film on KBr and measuring at a resolution of 2 cm-'. From formula [1], the infrared absorption peak ratio α, (2960)/α, (2925) of the a-C film is 0.
．． It was 92.

(II) (? (Formation of charge generation layer) High frequency power source (7
39) was temporarily stopped, and the inside of the reaction chamber was evacuated.

The fourth and second regulating valves (710) and (708) are opened, and S'r Ha gas is discharged from the fourth tank (704).
Output pressure gauge IK for H and gas from the second tank (702)
g/cm" into the mass flow controllers (716) and (714). The scale of each mass flow controller was adjusted to control the flow rate of SiH* to 90 sccm.
The flow rate of SHt was set at 210 sec, and the SHt was allowed to flow into the reaction chamber.

After each flow rate became stable, the internal pressure of the reaction chamber (7:L) was adjusted to 1.0 Torr.

When the gas flow rate is stable and the internal pressure is stable, turn on the high frequency power supply (
739) and apply 150W to the power application electrode (736).
electric power (frequency: 13.56 MHz) was applied to generate glow discharge. This glow discharge was performed for 40 minutes to form a 1 μm thick a-Si:H charge generation layer.

The obtained photoreceptor had an initial surface potential (VO) of -300vo
The half-reduction exposure amount E1/2 at lt is 0.25 (2ux・
It was sec. Furthermore, when an image was formed and transferred onto this photoreceptor, a clear image was obtained.

Example 2 (I) In the glow discharge decomposition apparatus shown in FIG. 14, first, the inside of the reaction chamber (733) was heated to
After creating a high vacuum of about r, the first and second regulating valves (70
7) and (70g), and open the first tank (701).
C5Hz gas from the second tank (702) and H gas from the second tank (702) were flowed into the mass flow controllers (713) and (714) under an output pressure gauge of I kg/cm2. Then, adjust the scale of each mass flow controller by 1 m, and
t Ht flow rate is 90 sec, t (t is 120 s
ecm and flowed into the reaction chamber (733). After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr. On the other hand, the conductive cylindrical substrate (752) has a diameter of 60u and a length of 2
A 80j11 aluminum tube is heated in advance to 200°C, and when the flow rate of each gas is stable and the internal pressure is stable, the high frequency power source (739) is turned on and the power application electrode (73
6) 100 watts of power (frequency 13.56M
Hz) was applied for about 7 hours, and an infrared absorption peak ratio α1/α was applied on the conductive cylindrical substrate (752).
A charge transport layer having a thickness of about 10 μI with 2(2960)/α and (2925) of 0.80 was formed.

(II) The application of power from the high frequency power source (739) was temporarily stopped, and the inside of the reaction chamber was evacuated.

Open the fourth and second regulating valves (710) and (70g), and output S i H gas from the fourth tank (704) and H gas from the second tank (702) to an output pressure gauge of 1 kg.
/cm" into the mass flow controllers (716) and (714). The scale of each mass flow controller was adjusted to adjust the flow rate of SiH to 90 sec.
The flow rate of SHt was set to 400 sec, and it was allowed to flow into the reaction chamber. After each flow rate stabilizes, the reaction chamber (733
) was adjusted so that the internal pressure was 1.0 Torr.

When the gas flow rate is stable and the internal pressure is stable, turn on the high frequency power supply (
739) and apply 150W to the power application electrode (736).
electric power (frequency: 13.56 MHz) was applied to generate glow discharge. This glow discharge was performed for 40 minutes to form a 1 μm thick a-8t:H charge generation layer.

The obtained photoreceptor has an initial surface potential (Vo) = -60
The half-decreased exposure amount E1/2 at 0 volt is 0.31+2
It was ux-sec. Furthermore, when an image was formed and transferred onto this photoreceptor, a clear image was obtained.

Example 3 CI) In the glow discharge decomposition apparatus shown in FIG. 13, first, the inside of the reaction chamber (733) was
After creating a high vacuum of about rr, open the first and second regulating valves (7
07) and (708), and open the first tank (701).
) from the second tank (702) and H gas from the second tank (702) into the mass flow controllers (713) and (714) under the output pressure gauge IKg/cm''.Then, the scale of each mass flow controller was adjusted. Then, C
The flow rate of H is 40 scc+n, and the flow rate of H is 50 scc.
m, and flowed into the reaction chamber (733). After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 0.8 Torr. On the other hand, as the conductive substrate (752), a 3x50x50mn+ aluminum plate was used and preheated to 300°C.
When the flow rate of each gas is stable and the internal pressure is stable, turn on the high frequency power supply (739) and apply 300W to the power application electrode (736).
Atts electric power (frequency 13.56 MH2) was applied to perform plasma polymerization for about 12 hours, and the conductive substrate (752 MH2
) above is the infrared absorption peak ratio α, (2960)/α 292
5) was 1.15, and a charge transport layer having a thickness of approximately 9 μm was formed.

(n) After stopping the application of power from the high-frequency power source (739) and sufficiently exhausting the interior of the reaction chamber, leakage occurred and the sample was taken out. Then, in another vacuum evaporation device, A s x S
1143 was laminated on the charge transport layer provided in step (I) using a resistance heating method to a thickness of about 3 μm.

The obtained photoreceptor has an initial surface potential (Vo) = + 6
Half-exposure ""'1/2 at 50 volts is 0.23
(2ux·sec) When an image was formed and transferred onto this photoreceptor, a clear image was obtained.

Example 4 (1) In the glow discharge decomposition apparatus shown in FIG. 14, first, the inside of the reaction chamber (733) is made into a high vacuum of about 10-6 Torr, and then the first to third regulating valves (707)
or 709), C, H, gas from the first tank (701), CH, gas, from the second tank (702),
Output pressure gauge I for H and gas from the third tank (7 (13))
Mass flow controller (713) under “Kg/cm”
or 715). Then, by adjusting the scale of each mass flow controller, the flow m of C, I-1,
Set the reaction chamber (733 sccm) to 55 sccm, CH4 to 60 sccm, and FIt to 100 sccm
) flowed into the interior.

After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 2.0 Torr. On the other hand, as the conductive cylindrical substrate (752), an aluminum tube with a diameter of 80 mm and a length of 320 mm is used, which is heated to 250°C in advance. Turn on the power supply (739) and connect the power application electrode (
736), 200 watts of power (frequency 13.
56MH2) was applied for about 3 hours to perform plasma polymerization for about 3 hours, and a layer with a thickness of about 5μ with an infrared absorption peak ratio α, (2960)/α, (2925) of 1°02 was formed on the conductive cylindrical substrate (752). A shoulder charge transport layer was formed.

(IT) The application of power from the high frequency power source (739) was temporarily stopped, and the inside of the reaction chamber was evacuated.

Open the fourth and third regulating valves (710) and (709), and output 5 il-14 gas from the fourth tank (704) and 1-1 t gas from the third tank (703) to the output pressure gauge I Kg/cm. ” under the mass flow controller (71
0) and (709). Adjust the scale of each mass flow controller to adjust the flow rate of SiH for 90 seconds.
ecm, the flow rate of H2 was set to 400 sec, and was allowed to flow into the reaction chamber.

Similarly, from the 5th tank (705), use Hl for 50p.
B t He gas diluted to pm concentration was
The influx was made. After each flow rate is stabilized, the reaction chamber (73
3) The internal pressure was adjusted to 1.0 Torr.

When the gas flow rate is stable and the internal pressure is stable, turn on the high frequency power supply (
739) and 1 to the cylindrical power application electrode (736).
A glow discharge was generated by applying a power of 50 W (frequency 13.56 MHz). This glow discharge was performed for 40 minutes to form a 1 μm thick a-9i:H charge generation layer.

The obtained photoreceptor had an initial surface potential (Vo) = +450vo
The half-decreased exposure amount E1/2 at lt is 0.25σux's
It was ec. Furthermore, when an image was formed and transferred onto this photoreceptor, a clear image was obtained.

Example 5 (I) In the glow discharge decomposition apparatus shown in FIG. 13, first, the inside of the reaction chamber (733) was heated to
After creating a high vacuum of about r, the sixth and seventh regulating valves (712
) and (725) were opened, and He gas from the sixth tank (706) and styrene gas from the first container (719) were allowed to flow into the mass flow controllers (71g) to 728).

The first container (719) is heated by the first heater (722) to
It was used heated to 0°C. Then, adjust the scale of each mass flow controller to increase the flow rate of styrene to 18
secm, and He was set to 30 secm and flowed into the reaction chamber (733). After each flow rate becomes stable, the internal pressure of the reaction chamber (733) becomes 0 and Start
It was adjusted so that On the other hand, as the conductive substrate (752), a 3x50x5 (1+i) aluminum plate is used and heated to 50°C in advance to stabilize the flow rate of each gas.
When the internal pressure is stable, turn on the low frequency power supply (741) and apply a power of I 50 watts to the power application electrode (736).
Plasma polymerization is carried out for about 40 minutes by applying a frequency of 30 K) Tz), and a layer of about 5 μm in thickness with an infrared absorption peak ratio α, (2960)/α 2925) of 0°85 is formed on the conductive substrate (752). A charge transport layer of debris was formed.

(■) The application of power from the low frequency power source (741) was temporarily stopped, and the inside of the reaction chamber was evacuated.

Open the fourth and third regulating valves (710) and (709), and output SiH and gas from the fourth tank (704), and H and gas from the third tank (703) through the output pressure gauge IKg/a.
mass flow controller (716) and (
715). Adjust the scale of each mass flow controller to set the flow rate of SiH< to 90 sec, H
, was set at 210 sec to flow into the reaction chamber. After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.

When the gas flow rate is stable and the internal pressure is stable, turn on the high frequency power supply (
739) and applied 150W to the power application electrode (73B).
electric power (frequency: 13.56 MH2) was applied to generate glow discharge. This glow discharge was performed for 40 minutes to form a 1 μm thick a-9i:H charge generation layer.

The obtained photoreceptor had an initial surface potential (Vo)=-so.

The half-decreased exposure amount Et 72 at the time of volt is 0.39 (2
It was ux-sec. Furthermore, when an image was formed and transferred onto this photoreceptor, a clear image was obtained.

Example 6 (1) In the glow discharge decomposition apparatus shown in FIG. 14, first, the inside of the reaction chamber (733) was heated to
After creating a high vacuum of about r, open the first to third regulating valves (70
7) Open or 709) and remove the first tank (701).
C2H4 gas from the second tank (702), butadiene gas from the second tank (702), and F (2 gases) from the third tank (703).
713) or 715). Then, adjust the scale of each mass flow controller to obtain Ct H4.
Flow rate of 55 sec, Butadiene 55 sec,
Set Ha to 101005e and prepare the reaction chamber (
733). After each flow m became stable, the internal pressure of the reaction chamber (733) was adjusted to 1.5 torr.

On the other hand, the conductive cylindrical substrate (752) has a diameter of 80 mm.
Using an aluminum tube with a length of 5 mm and a length of 320 mm.
Preheat to 0°C, and with each gas flow rate stabilized and internal pressure stabilized, turn on the high frequency power supply (739) and apply 200 watts of power (frequency 13.56MHz) to the power application electrode (736). was applied for about 12 hours, and the infrared absorption peak ratio α, (2960)/α, (2925) was 1.
A charge transport layer having a thickness of approximately 20 μm was formed.

([1) The application of power from the high frequency power source (739) was temporarily stopped, and the inside of the reaction chamber was evacuated.

The fourth and third regulating valves (710) and (709) are opened, and SiHa gas is supplied from the fourth tank (704) and the third
Output pressure gauge IKg/H gas from tank (703)
cm'' into the mass flow controllers (716) and (715). Adjust the scale of each mass flow controller to adjust the flow rate of 5IH4 to 90 sccmSH.
The flow rate of z was set to 300 sec and flowed into the reaction chamber. After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.

When the gas flow rate is stable and the internal pressure is stable, turn on the high frequency power supply (
739) and 150W to the cylindrical electrode plate (752).
electric power (frequency: 13.56 MHz) was applied to generate glow discharge. This glow discharge was performed for 40 minutes to form a 1 μm thick a-Si:H charge generation layer.

The obtained photoreceptor had an initial surface potential (Vo) = -600vo
Half exposure at lt is 0.3012ux
-88C. Furthermore, when an image was formed and transferred onto this photoreceptor, a clear image was obtained.

Example 7 (T) In the glow discharge decomposition apparatus shown in FIG. 13, the inside of the reaction chamber (733) was heated to 10-' Torr.
After creating a high vacuum of about r, open the first or second regulating valve (70
7) Open or 708) and remove the first tank (701).
C1H4 gas from the second tank (702) and H gas from the second tank (702) were flowed into the mass flow controller (713) or 714) under the output pressure gauge IKg/cn+'.

Then, adjust the scale of each mass flow controller,
The flow rate of C, I-I, is 180 secSI-1t is 2
The reaction chamber (733) was set to 40 sec.
It flowed inside.

After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 0.5 torr. On the other hand, as the conductive substrate (752), a 3 x 50 x 50 x m aluminum plate was used and preheated to 250°C.
When the flow rate of each gas is stable and the internal pressure is stable, turn on the high frequency power supply (739) and apply 500% to the power application electrode (736).
watts power (frequency 13, 56 MI-rz)
was applied for about 6 hours, and an infrared absorption peak ratio α, (2960)/
α.

A charge transport layer having a thickness of approximately 18 μm and having (2925) of 0.70 was formed.

(II) After stopping the application of power from the high-frequency power source (739) and sufficiently exhausting the inside of the reaction chamber, leakage occurred and the sample was taken out. Next, in another vacuum evaporation device, As25ex was heated to a thickness of about 3 μm using a resistance heating process (step 1).
) was laminated on the charge transport layer provided in ( ).

The obtained photoreceptor had an initial surface potential (Vo) = +600vo
Half-exposure ""l/2 at lt is 1,5 Qux
・It was sec. Although the sensitivity was slightly lower than that of Examples 1 to 6, a sensitivity with no practical problems was obtained.

Furthermore, when an image was formed and transferred onto this photoreceptor, a clear image was obtained.

Example 8 (1) In the glow discharge decomposition apparatus shown in FIG. 14, first, the inside of the reaction chamber (733) was
After making the vacuum as high as possible, open the first to third regulating valves (707
) or 709), CyHa gas is supplied from the first tank (701), and Cs Hs is supplied from the second tank (702).
Gas, Ht gas is supplied from the third tank (7 (13)) to the mass flow controller (under the output pressure gauge 11 [g/cm').
713) or 715). Then, adjust the scale of each mass flow controller to obtain C, tI4.
Flow rate of a is 30sec, C5Ha is 305ccn+S
H, was set to 1005ccn+ and flowed into the reaction chamber (733).

After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 0.8 torr. On the other hand, as the conductive cylindrical substrate (752), an aluminum tube with a diameter of 80+ nm and a length of 320 mm is preheated to 60°C, and when the flow rate of each gas is stable and the internal pressure is stable, high frequency Turn on the power supply (739) and connect the power application electrode (736).
) with 200 watts of power (frequency 13.56 M
Plasma polymerization is performed for about 15 hours by applying tl Z), and a layer is formed on the conductive cylindrical substrate (752) to a thickness such that the infrared absorption peak ratio α, (2960)/α, (2925) is 1.30. A charge transport layer with a thickness of 20μ was formed.

(II) The application of power from the high frequency type R (739) was temporarily stopped, and the inside of the reaction chamber was evacuated.

The fourth and third regulating valves (710) and (709) are opened, and SiH and gas are supplied from the fourth tank (704), and H and gas are supplied from the third tank (703) using an output pressure gauge of 1 kg/c.
mass 70-controller (716) and (
715). Adjust the scale of each mass flow controller to set the flow rate of 5IH4 to 100 seconds,
The flow rate of Ht was set to 4 Q Osccm and was allowed to flow into the reaction chamber. After each flow rate stabilizes, the reaction chamber (733
) was adjusted so that the internal pressure was 0.8 Torr.

When the gas flow rate is stable and the internal pressure is stable, turn on the high frequency power supply (
739) and apply 150W to the power application electrode (736).
electric power (frequency: 13.56 MHz) was applied to generate glow discharge. This glow discharge was performed for 35 minutes to form a 1 μm thick a-Si:H charge generation layer.

The obtained photoreceptor had an initial surface potential (Vo) = -400vo
Half exposure "1/2" at lt is 0.52 Qux Se
It was C. Although the charging ability was lower compared to Examples 1 to 6 in relation to the film thickness, characteristics with no problems in practical use were obtained. Furthermore, when an image was formed and transferred onto this photoreceptor, a clear image was obtained.

Example 9 CI) In the glow discharge decomposition apparatus shown in FIG. ) was opened, and H and gas were allowed to flow from the first tank (701), and C, 8, and 4 gases were allowed to flow from the first container (719)) into the mass flow controllers (713) to 728). The first container (719) was heated to about 70° C. by the first heater (722) before use. Then, adjust the scale of each mass flow controller to increase the flow m of H by 3
00sccm and Ce1-(+4 were set to 30sec and flowed into the reaction chamber (733). After each flow rate became stable, the internal pressure of the reaction chamber (733) decreased to 0.3
I adjusted it so that it would be torr. On the other hand, a conductive substrate (7
As for 52), use an aluminum plate of 3 x 50 x 50 x m and preheat it to 30°C, and when the flow rate of each gas is stable and the internal pressure is stable, turn on the high frequency power supply (739) and connect the power application electrode (736). A power of 50 watts (frequency 13.56 M, iZ) was applied to perform plasma polymerization for about 6 hours, and an infrared absorption peak ratio α, (2960)/α, (2925) was formed on the conductive substrate (752). is 1.
A charge transport layer having a thickness of about 18 microns was formed.

(n) The application of power from the high frequency power source (739) was temporarily stopped, and the inside of the reaction chamber was evacuated.

Open the fourth and third regulating valves (71(1) and (709), and output SiH4 gas from the fourth tank (704) and H gas from the third tank (703) to the output pressure gauge IKg.
/cm" into the mass flow controllers (716) and (715). The scale of each mass flow controller was adjusted to adjust the flow rate of SiHa to 90 sec.
The flow rate of Ht was set at 180 sec, and the Ht was allowed to flow into the reaction chamber. Similarly, BtHa gas diluted to 50 ppma with H3 from the fifth tank (705) was IO.
sccm inflow. After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.

When the gas flow rate is stable and the internal pressure is stable, turn on the high frequency power supply (
739) and apply 170W to the power application electrode (736).
A glow discharge was generated by applying electric power (frequency 13, 56 Ml-1z). This glow discharge was performed for 30 minutes to form a 1 μm thick a-Si:H charge generation layer.

The obtained photoreceptor has an initial surface potential (V O) = + 3
The half-decreased exposure amount El/2 at 50 volts is 0.49Q
It was ux-sec. Although the charging ability per unit film thickness was lower than that of Examples 1 to 8, performance capable of contributing as an electrophotographic photoreceptor was obtained. Further, when an image was formed and transferred onto this photoreceptor, an image was obtained.

Example 10 (I) In the glow discharge decomposition apparatus shown in FIG. 14, first, the inside of the reaction chamber (733) was heated to
After creating a high vacuum of about r, open the first to third regulating valves (70
7) Open or 709) and remove the first tank (701).
From C, I-1, gas, from the second tank (702) CH
, gas, and H gas from the third tank (703) under the output pressure gauge IKg/cm' of the mass flow controller (703).
13) or 715). Then, by adjusting the scale of each mass flow controller, C, I-t,
The flow rate of CH4 is 200 sec, and the flow rate of CH4 is 180 sec.
, I(t) was set to 100 seconds and flowed into the reaction chamber (733).

After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 2.0 Torr. On the other hand, the conductive cylindrical substrate (752) has a diameter of 80 mm and a length of 3 mm.
A 20n+m aluminum tube is preheated to 300°C, and when the flow rate of each gas is stabilized and the internal pressure is stable, the high frequency power source (739) is turned on and the power application electrode (73
6) 300 watts of power (frequency 13゜56MH)
z) to perform plasma polymerization for about 2 hours, and infrared absorption peak ratio α, (2
960)/α2925) is 0.5, about 10 μl thick.
A charge transport layer was formed.

(II) The application of power from the high frequency power source (739) was temporarily stopped, and the inside of the reaction chamber was evacuated.

Open the fourth and third regulating valves (710) and (709), and output SiH4 gas from the fourth tank (704) and H gas from the third tank (703) using the output pressure gauge IKg/c.
a+" into the mass flow controllers (716) and (715). Adjust the scale of each mass flow controller to adjust the flow rate of SiH4 to 1 20 sccr.
a, The flow rate of H* was set to 400 sec, and it was allowed to flow into the reaction chamber. Similarly, 12 sccn+ of B t Hs gas diluted with H8 to 50 ppmet was introduced from the fifth tank (705). After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.

When the gas flow rate is stable and the internal pressure is stable, turn on the high frequency power supply (
739) and 200W to the cylindrical electrode plate (752).
electric power (frequency: 13.56 MHz) was applied to generate glow discharge. This glow discharge was performed for 30 minutes to form a 1 μm thick a-8i:II charge generation layer.

The obtained photoreceptor has an initial surface potential (V o) = + 4
The half-decreased exposure amount El/2 at 50 volts is lQ, 3(
It was 2ux-sec. Although the sensitivity was lower than in Examples 1 to 8, performance capable of contributing as an electrophotographic photoreceptor was obtained. Further, when an image was formed and transferred onto this photoreceptor, an image was obtained.

Comparative Example 1 The step (formation of IXa-C layer) in Example 1 was omitted, and an a-9i:H layer with a film thickness of 6 μm was formed under the same conditions as step (n), and an a-Si:H photoreceptor was formed. Obtained.

The obtained photoreceptor had an initial surface potential (Vo) of -100V and a half-life exposure @E1/2 of Q, 7 Lux-sec, and did not exhibit sufficient charging ability with ten polarity, making it impossible to form a good image. Ta.

It was understood that the charge transport layer according to the present invention significantly contributes to improving charging ability and has suitable transport properties.

Comparative Example 2 Instead of the charge transport layer according to the invention prepared in step (r) of Example 1, α, (2960)/α, (2925)
A polyethylene film having a ratio of 0.15 was prepared by a conventional method of organic polymerization, and step (n) was performed thereon. The obtained laminated film differs from the present invention only in the infrared absorption peak ratio. Although the charging ability is the same as in Example 1, the sensitivity is a −
To the extent that there is a slight potential attenuation due to the S4 layer,
This did not reach the half-reduced value. The superiority of the charge transport layer of the present invention was recognized.

Comparative Example 3 (1) In the glow discharge decomposition apparatus shown in FIG. 14, first, the inside of the reaction chamber (733) was heated to 10-@Torr.
After creating a high vacuum of about
7) Open the first tank (701)
More C! H, gas was flowed from the second tank (702) into the mass flow controller (713) or 714) under the output pressure gauge IKg/am". Then, the scale of each mass flow controller was adjusted. T,C
,H.

Flow rate of 250 sccm, ! -1, 350 se
cm, and flowed into the reaction chamber (733). After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 0.5 torr. On the other hand, as the conductive cylindrical substrate (752), an aluminum tube with a diameter of 80 mm and a length of 320 mm is used, which is heated to 2508C in advance, and when the flow rate of each gas is stable and the internal pressure is stable, a high frequency power source is applied. (739) and power application electrode (
736) with 500 watts of power (frequency 13.5
6 MHz) to perform plasma polymerization for about 2 hours,
On the conductive cylindrical substrate (752), the infrared absorption peak ratio α
, (2960)/α, and (2925) of 0.45, a charge transport layer having a thickness of approximately 7 μl was formed.

(II) The application of power from the high frequency power source (739) was temporarily stopped, and the inside of the reaction chamber was evacuated.

Open the fourth and third regulating valves (710) and (709), and output SiH and gas from the fourth tank (704), and H and gas from the third tank (703) through the output pressure gauge IKg/c.
mass 70-controller (716) and (
715). Adjust the scale of each mass flow controller to adjust the flow rate of 5IH4 to 90secSH,
The flow rate was set at 400 sec, and the mixture was allowed to flow into the reaction chamber.

After each stream 1 became stable, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.

When the gas flow rate is stable and the internal pressure is stable, turn on the high frequency power supply (
7:19) and applied 150 to the power application electrode (L12).
A glow discharge was generated by applying a power of W (frequency: 13.56 MHz). This glow discharge was performed for 40 minutes to form a 1 μm thick a-9t:H charge generation layer.

The obtained photoreceptor has an initial surface potential of (V o) = −3
It was understood that even if image exposure was carried out at 50 volts, the half potential could not be reached, and that the photoreceptor could not be used as an electrophotographic photoreceptor.

Comparative Example 4 (I) In the glow discharge decomposition apparatus shown in FIG.
After creating a high vacuum of about rr, open the first and seventh regulating valves (70
7) and (725) were opened, and H and gas from the first tank (701) and styrene gas from the first container (719) were allowed to flow into the mass flow controllers (71, 3) and (728).

The first container (719) is heated by the first heater (722) to
It was used heated to 0°C. Then, adjust the scale of each mass flow controller to adjust the flow rate of H to 60 s.
cc+n, and styrene was set to 60 sccm and flowed into the reaction chamber (733). After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 0.8 Torr. On the other hand, as the conductive substrate (752), use an aluminum plate of 3 x 50 x 50 juts, preheat it to 50°C, and turn on the low frequency power supply (741) when the flow rate of each gas is stable and the internal pressure is stable. Then, 150 watts of power (frequency 100 KH2) was applied to the power application electrode (736) to perform plasma polymerization for about 50 minutes, and the infrared absorption peak ratio α,
(296Q)/αt(2925) is 16 and the thickness is approximately 10
A charge transport layer of μ scrap was formed.

At this time, a considerably rough film quality was observed.

(U) The application of power from the low frequency power source (741) was temporarily stopped, and the inside of the reaction chamber was evacuated.

The 4th and 37A regulating valves (710) and (709) are opened, and SiH, gas, and
Output pressure gauge IKg/H2 gas from tank (703)
cm'' into the mass flow controllers (716) and (715).The scale of each mass flow controller was adjusted to adjust the flow rate of SiH to 90 sccm SH.
The flow rate at t was set to 200 sec, and the sample was allowed to flow into the reaction chamber. Similarly, B t Ha gas diluted with H3 to a concentration of 50 ppm was supplied from the fifth tank (705) to 101
05e flowed in. After each flow rate became stable, the internal pressure of the reaction chamber (733) was adjusted to 1.0 Torr.

When the gas flow rate is stable and the internal pressure is stable, turn on the high frequency power supply (
739) and the power applying electrode (7:(6) to 150
A glow discharge was generated by applying a power of W (frequency: 13.56 MI-(Z)). This glow discharge was carried out for 40 minutes to form an a-St:H charge generation layer having a thickness of 1 μm.

The obtained photoreceptor has an initial surface potential of (Vo)=+20vo
It is understood that the photoreceptor did not have the performance as a photoreceptor because it was only lt and peeling occurred partially.

Effects of the Invention The photoreceptor in which the organic plasma polymerized film of the present invention is used as a charge transport layer has excellent charge transport properties and charging ability, can obtain a sufficient surface potential even with a thin film thickness, and can produce good images. You can get it. According to the present invention, the charge generation layer includes a-5i.
When using this method, it is possible to obtain a thin film photoreceptor that could not be achieved with conventional a-9i photoreceptors.

In the photoreceptor of the present invention, the raw materials thereof are inexpensive, each necessary layer can be formed in the same tank, and the film thickness may be thin, so that the manufacturing cost is low and the manufacturing time is short. The organic plasma polymerized film according to the present invention is difficult to form pinholes even when formed into a thin film, and can be formed homogeneously, so that it can be easily made into a thin film. In addition, corona resistance, acid resistance,
It also has excellent moisture resistance, heat resistance, and rigidity, so when used as a surface protective layer, it improves the durability of the photoreceptor.

[Brief explanation of drawings]

1 to 12 show schematic cross-sectional views of the photoreceptor of the present invention. FIG. 13 and FIG. 14 are diagrams showing an example of an apparatus for manufacturing a photoreceptor. FIG. 15 is a diagram showing an infrared absorption spectrum of the a-C layer. The symbols in the figure are as follows. (1)...Substrate (2)...Charge transport layer (a
-C layer) (3)...charge generation layer (4)...overcoat layer (5)...undercoat layer (701) to (706)...tank (707) to (712) and (725) ~ (727)・
...Control valves (713) to (71g) and (728) to (
730)...1llll1111W (mass flow controller) (719) to (721)... Container (722
) ~ (724)... Heater (731)... Mixer
(732)...Main pipe (733)...Reaction chamber
(734)...Pipe heater (735)...Ground electrode (736)...Power application electrode (737)...
Power heater (738)...High frequency power matching device (73
9)...High frequency power supply (740)...Low frequency power matching box (741)...Low frequency power supply (742)...Low pass filter (743)...DC power supply (744)...
... Connection selection switch (745) ... Pressure control valve (
746)...Exhaust system selection valve (747)...Diffusion pump (74g)...Oil rotary pump (749)...Cooling exclusion device (750)...Mechanical booster pump (751)
... Reaction heater (752) ... Conductive substrate (75
3)...Engraving of excluded equipment drawings (no changes in content) ° 11th! I 21st! I
@3 Figure 4 Figure 5 $6rM 7th f! Il! Figure 8 9'! ! 1
Figure 1110 $11111 11123!
115t! 1 Additional number (cm”)

Claims (1)

[Claims] 1. In a functionally separated photoreceptor having a charge generation layer (3) and a charge transport layer (2), a hydrocarbon plasma polymerized film is provided as the charge transport layer (2), and the infrared absorption spectrum of the polymerized film is 2960cm^ due to methyl (-CH_3) group
The peak absorption coefficient α_1 near -^1 and methylene (-CH
The ratio α_1/α_2 to the peak absorption coefficient α_2 near 2925 cm^-^1 due to the _2-) group is 0.5 to 1.
5. A photoconductor characterized in that: