JPS6381364A - Manufacture of electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic sensitive body having high acceptance potential and capable of forming an image with a small electrically charging current and a small amount of exposure light energy by forming as a charge transfer layer a film composed essentially of carbon by using a combination of a carbon compound containing halogen and a reducing agent as a main material. CONSTITUTION:A photosensitive layer is obtained by laminating on a substrate 14 a charge generating layer 12 and the charge transfer layer 13 of a film composed essentially of carbon made from a combination of the carbon compound containing halogen and the reducing agent as the main material. It is preferred for said film to contain at least one of H, N, and O, thus permitting the obtained electrophotographic sensitive body to have high acceptance potential and to form an image with a small charging current and a small amount of exposure light energy.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an electrophotographic photoreceptor used in an electrophotographic apparatus.

(Prior Art) Conventionally, the photoconductive layer of an electrophotographic photoreceptor is composed of an inorganic photoconductive material such as A-5e (amorphous Cele), CdS, ZnO, and A-5i (amorphous silicon). or charge transfer chains of poly-N-vinylcarbazole (PVK) and trinitrofluorenone (TNF), systems containing triphenylmethane derivatives and thiapyrylium salts in polycarbonate, and organic pigments such as disazo pigments and phthalocyanine pigments. It is common to have a laminated structure of a charge generation layer containing a material, etc., and a charge transport layer containing an electron donating molecule such as a hydrazone derivative or a triphenylamine conductor in an organic polymer.

[Problem that the invention seeks to solve]

However, there are still various problems to be solved in electrophotographic photoreceptors using these photoconductive materials.

For example, in an electrophotographic photoreceptor using A-5e as a material for forming a photoconductive layer, if Se is used alone, its spectral sensitivity range is biased towards the short wavelength side of the visible range, so the range of application is limited. Therefore, attempts have been made to widen the spectral sensitivity range by adding Te or As. However, although the electrophotographic photoreceptor having such a Se-based photoconductive layer containing Te or As improves its spectral sensitivity range, it suffers from increased optical fatigue, decreased chargeability in high-temperature environments, or problems in low-temperature environments. There were problems such as an increase in the residual potential in the wafer, resulting in a decrease in image quality and a loss of stability during repeated use. Moreover, Se%As%Te
In particular, since As and Te are extremely harmful substances to the human body, it was necessary to devise ways to use manufacturing equipment that would not come into contact with the human body during manufacturing. In addition, when blade cleaning is applied because the photoconductive layer has low hardness and is superior in cleaning reliability and miniaturization of the device, if the surface of the photoconductive layer is exposed, the surface of the photoconductive layer is directly rubbed, resulting in
A portion of the particles may be scraped off and mixed into the developer, or may be scattered into the copying machine or mixed into the copied image, resulting in contact with the human body. Also, Se
has a low crystallization temperature, so it easily crystallizes with a little heating or light irradiation, which can cause a decrease in chargeability.

On the other hand, in electrophotographic photoreceptors that use ZnO, CdS, etc. as photoconductive layer constituent materials, the photoconductive layer is generally made of Zn.
It is formed by uniformly dispersing photoconductive material particles such as O or CdS in a suitable resin binder.

However, when using ZnO, it requires spectral sensitization such as adding an organic pigment to make it sensitive to visible light, or the sensitivity decreases with repeated use, so it is not used in large numbers. It could not be used repeatedly. Also, unlike ZnO, CdS has an effect on the human body, so when using CdS, it is necessary to prevent it from coming into contact with the human body or scattering into the surrounding environment during manufacturing and use. was there. Furthermore, binder-based photoconductive layers are difficult to use due to the specificity that the photoconductive material particles must be uniformly dispersed in the resin binder, as well as the electrical and photoconductive properties of the photoconductive layer and the physical and chemical properties of the photoconductive layer. There are many parameters that determine the characteristics, and unless these parameters are precisely adjusted, it is not possible to form a photoconductive layer with desired characteristics with good reproducibility, resulting in a decrease in yield and a lack of mass productivity. Ta. In addition, due to the unique nature of the binder-based photoconductive layer being a dispersed system, the entire layer is porous and has a significant humidity dependence, resulting in deterioration of electrical properties when used in a humid atmosphere, making it difficult to obtain high-quality copied images. There were also problems, such as in many cases not being obtained.

In addition, electrophotographic photoreceptors that use organic materials such as PV/TNF charge transfer chains, organic pigments, electron-donating molecules, or organic polymers have low corona ion resistance, so their characteristics may change during use. It is difficult to use while maintaining high image quality over a long period of time due to problems such as deterioration, cleaning problems due to the use of organic polymers like toner, and easy scratching of the surface due to low mechanical strength. There were many things. Furthermore, although it is possible to design molecules relatively freely, in reality, for example, in the case of a charge transport layer, there are considerable restrictions on the binder polymers that can be used due to poor compatibility between electron donating molecules and binder polymers. There were problems such as. Furthermore, many of the electron-withdrawing molecules and electron-donating molecules that are widely used among these organic photoconductive materials are harmful to the human body, and many of them are carcinogenic. Constraints were also often a major obstacle in actual material selection.

[Purpose of the invention]

As a result of intensive research, the present inventors have conducted extensive research in order to obtain an electrophotographic photoreceptor that eliminates the various drawbacks of the conventional electrophotographic photoreceptor described above.
The present invention was completed based on the discovery that excellent characteristics as an electrophotographic photoreceptor can be obtained by forming the charge transfer layer of a functionally separated electrophotographic photoreceptor with a film mainly composed of carbon.

That is, an object of the present invention is to provide an electrophotographic photoreceptor that has high charging ability and can form images with a small charging current and a small amount of exposure energy.

Another object of the present invention is to provide an electrophotographic photoreceptor capable of high-speed image formation.

Still another object of the present invention is to provide an electrophotographic photoreceptor that can easily produce high-quality images with high density, clear halftones, and high resolution.

Still another object of the present invention is to provide an electrophotographic photoreceptor that can maintain stable images against changes in the usage environment such as temperature and humidity.

Still another object of the present invention is to reduce the influence of corona discharge products and paper dust during repeated use, and to enable continuous use while maintaining stable images for a long period of time without damaging the surface. Our purpose is to provide electrophotographic photoreceptors.

Still another object of the present invention is to prevent chemical changes, deterioration, crystallization, and other changes in the photosensitive layer, withstand long-term storage in adverse environments, and reproduce the same good image quality as before storage. The purpose of the present invention is to provide an electrophotographic photoreceptor that can perform various functions.

Still another object of the present invention is that there is no harm to the human body even if it comes into contact with the human body during the manufacturing process or when handling it in an office, etc., and that there is no risk of a part of the photosensitive layer being scraped and mixed into the developer. It is completely safe even if it is included in the toner image on the copy and comes into contact with the human body, and if necessary, it can be disposed of with some garbage after use, and there is no safety problem at all. To provide an electrophotographic photoreceptor that can be used safely without special precautions, does not emit toxic gas even if burned together with other materials in an emergency such as a fire, and is therefore completely safe in all respects. It is in.

Still another object of the present invention is that it can be manufactured without using harmful raw materials or with an extremely small amount of harmful raw materials compared to conventional methods, and for this reason, it is possible to manufacture the It is an object of the present invention to provide an electrophotographic photoreceptor that can significantly reduce the cost required for a harmful substance removal device and other manufacturing safety measures.

Still another object of the present invention is to provide a low-cost electrophotographic photoreceptor that can use readily available and inexpensive raw materials for manufacturing.

Still another object of the present invention is to eliminate the need for complex processes such as mixing and dispersing non-uniform materials or controlling particle size distribution, and to prevent interlayer contamination that occurs during preparation of coating liquids, viscosity control during coating, and multilayer structures. It is an object of the present invention to provide an electrophotographic photoreceptor that can be manufactured by a simplified process that does not require processing of solvents or solvent exhaust, and can be manufactured using manufacturing equipment that is easy to maintain.

Still another object of the present invention is to eliminate the generation of fine particles due to non-formation of fine powder during manufacturing or peeling off of a film adhering to the inside of the manufacturing container.
It is an object of the present invention to provide an electrophotographic photoreceptor that can stably obtain a defect-free and uniform photosensitive layer for a long period of time.

[Means for solving problems]

The above object of the present invention is to provide a method for producing an electrophotographic photoreceptor having a photosensitive layer in which a charge generation layer and a charge transport layer are laminated on a support, the charge transport layer being reduced with a carbon compound containing a halogen atom. This is achieved by an electrophotographic photoreceptor characterized by having a step of forming a film mainly composed of carbon using a combination of a carbonaceous agent as a main raw material and a carbon-based film.

In the present invention, the carbon-based film is, for example, a hydrocarbon-based highly insulating linear organic polymer such as polyethylene, or a low-resistance graphite polycrystalline film such as a vacuum-deposited graphite film made of carbon atoms. It has very different characteristics.

The object of the present invention is not achieved with such conventional carbon membranes. The reason for this is that when an organic polymer containing a large amount of hydrogen, such as the above-mentioned polyethylene, is used in the charge transport layer, although it may be possible to improve the charging ability, the sensitivity to light in the visible and near-infrared regions decreases. This is because there is little to be gained.

Further, if the graphite polycrystalline film is used, the charging ability is lowered and a practical electrophotographic photoreceptor cannot be obtained.

The film mainly composed of carbon in the present invention is single crystal, polycrystal,
It may take any form of an amorphous phase or a mixed phase of these phases, but preferably at least its electrical conductivity σ. It is desirable that the film has a hydrogen concentration of 40 at % or less, and an optical band gap Egopf of 1.5 eV or more.

The present invention is based on the discovery of a phenomenon in which a film mainly composed of carbon having the above-mentioned physical properties is highly insulating, but when charges are injected into the layer, the injected charges are transported by an electric field. , and such carbon-based films cannot be manufactured using conventional manufacturing conditions. In general, the conduction form of charge in an electrophotographic photoreceptor is quite dependent on the film formation conditions, and the film formation conditions that can produce clean band conduction are not necessarily wide, and in many cases, a transient current waveform with a strong dispersion type character is obtained. This also applies to the present invention, but the carbon-based film of the present invention can be fully used as an electrophotographic photoreceptor even in such a state.

By the way, in the past, a layer mainly composed of a-Si or a-Ge with carbon added thereto was used as one of the constituent layers of an electrophotographic photoreceptor.
An example of using it as one is JP-A-54-55439.
, JP 55-4040, JP 55-49304, JP 56-121041. Examples include JP-A No. 60-26345, JP-A No. 61-94048, JP-A No. 61-94049, and JP-A No. 61-105551. But these are a-
The film properties are improved by adding carbon while maintaining the functions obtained from 5i or a-Ge, and do not utilize the functions obtained by making carbon the main component. That is, firstly, the carbon-based film of the present invention (hereinafter referred to as "carbonaceous film") contains the above-mentioned Si.
or Ge should not be included, or even if included, should be kept as small as possible. Furthermore, the film formation conditions used in the above proposals are those applied when forming the a-5i and a-Ge layers, and the purpose of the present invention cannot be achieved under such conditions. It is not possible to create a film that does this.

The carbonaceous film in the present invention is produced under conditions and specific conditions that allow the formation of a carbonaceous film having the specific properties and characteristics described above, for example, by a vapor phase film-forming method using a carbon compound and hydrogen molecules as raw materials. Specifically, the film formation conditions are set as described in Examples described later. The setting of this condition was made for the first time by the present inventor. The mechanism of film formation is not necessarily clear, but it occurs during film formation by giving energy to the raw material gas molecules by discharging the raw material gas or heating the raw material gas, or by hitting the substrate being deposited with accelerated electrons. Accelerating ions with an electric field or applying a magnetic field to the plasma generation region are effective in obtaining the carbonaceous film as referred to in the present invention.

The carbon-based film of the present invention is produced by vapor phase film formation using a combination of a carbon compound containing a carbon-halogen atom bond and a compound capable of breaking the carbon-halogen atom bond, that is, a reducing agent, as the main raw materials. create. Various vapor phase film forming methods can be used.

A film can be formed on a substrate by imparting energy to molecules in the raw material gas through plasma generated by discharge of the raw material gas, thermal decomposition of the raw material gas, light irradiation of the raw material gas, and the like.

At present, we do not know much about the mechanism of film formation, but the phenomenon is that when the main raw material is a combination of a carbon compound containing a carbon-halogen atom bond and a reducing agent capable of cutting the carbon-halogen atom, The types of carbon-carbon bonds contained in the obtained carbon film tended to be limited.

A carbon compound containing a carbon-halogen atom bond (:F,
As a result of examining various excitation methods using the same device using a combination of H2 as the i-based agent as the main raw material, the details of the reaction are unknown, but the carbon-carbon bonds contained in the obtained carbon film are C
There was a tendency for the number of C-C double bonds to decrease compared to when I+4 was used as the main raw material, and there were also cases where F remained in the film.

In addition, the ratio of the number of F atoms incorporated into the film to the number of C atoms (F/C) changes by changing the gas flow rate ratio,
Along with this, there was a tendency for the density of the film to change significantly.

The ratio of the number of F atoms incorporated into the film to the number of C atoms is ES(:A (Electron 5pectros
copy for Chemical Analysis
).

FIGS. 1 and 2 show the most typical structural example of an electrophotographic photoreceptor according to the present invention. In these figures, those indicated by numerals 13 and 23 are charge transport layers made of carbonaceous films according to the present invention. 12 and 22 are charge generation layers, 14 and 24 are supports, 11 is a surface layer, and 21 is a charge injection blocking layer.

It is not preferable for the charge transport layers 13 and 23 to contain a large amount of hydrogen atoms, and the content of hydrogen atoms is 40 atomic %.
Hereinafter, it is preferably 30 atomic % or less. This is because too large an amount of hydrogen atoms causes a decrease in photosensitivity, an increase in residual potential, or a tendency to scratch the surface. However, since the inclusion of hydrogen atoms in the film is effective in improving chargeability and reducing residual potential, it is preferable to set the lower limit to 0. O
It is desirable that the number of atoms be 11. .

In addition to the above hydrogen atoms, the carbonaceous film constituting the charge transport layer may also contain halogen atoms (X) such as fluorine and chlorine, and nitrogen atoms, and these atoms also have the same properties as the above hydrogen atoms. effective. Furthermore, the inclusion of oxygen atoms is also effective in improving charging properties. In addition, charge transport layers 13 and 2
3 is 1O-IfΩ-1c because if its electrical conductivity is too high, it may cause a decrease in chargeability or a blurred image.
It is preferable that it is less than c1. Furthermore, charge transport layer 13
and the optical band gap Eg- of 23 is 1.5 eV
The above value is preferably 2.0 OeV or more. Particularly in the case of the configuration shown in FIG. 2, it is desirable that the optical bandgap be 2.5 eV or more.

The carbonaceous films constituting the charge transport layers 13 and 23 may be amorphous or may contain a crystalline phase. In particular, it is desirable to at least partially include a structure characterized by Stokes lines in a region including 1333 cm' of the Raman spectrum. If the carbonaceous film constituting the charge transport layer is close to polycrystalline diamond containing a large amount of perfect diamond structure, it may become colored depending on the electrophotographic photoreceptor's chargeability, sensitivity, surface hardness, and resistance. However, irrespective of whether the resulting film is amorphous or crystalline, coloring can be reduced, for example, by increasing the flow rate ratio of hydrogen or halogen during film formation.

As the carbonaceous film semiconductor impurity constituting the charge transport layers 13 and 23, the characteristics can be improved by performing dobin enrichment with atoms belonging to group I or group V of the periodic table. Such doping with Group M or Group V has the effect of increasing charging properties, improving sensitivity, and lowering residual potential when the electrophotographic photoreceptor of the present invention is used with positive or negative charging. This is considered to be because the concentration of charge carriers in the charge transport layers 13 and 23 changes due to doping with these atoms, or the transportability of charge carriers changes. Since this change is relatively gradual, it is easy to control. The amount of these atoms added is preferably 5
It is desirable that the content be in the range of ppm or more and 5 atomic % or less, and more preferably 50 ppm or more and 1 atomic % or less. These conditions will be described in more detail in the Examples. Atoms belonging to group m include B, AI, Ga, In, TI
etc. Group V atoms include N, P,
Examples include As, Sb, Bi, etc.

N from the viewpoint of manufacturing stability, cost, size of effect, etc.
Particularly desirable are P, B, AI, etc.

The thickness of the charge transport layers 13 and 23 can be appropriately selected depending on the conditions of use, etc., but is preferably 1p or more and 100J.
It is desirable that it be between Aj and below. If it is less than 1μ, it may not be possible to obtain a satisfactory visual density using normal development methods, while if it is more than 100p, the residual potential may be too large, the time required for film formation may be too long, or the film may not be compatible with the support. This is because it may cause problems with the adhesion of the film. A more preferable range of the layer thickness is 5p or more and 50
less than In this range, the usage conditions are not only easy to use, but also the image density tends to be higher even if the film thickness is thinner than that of conventional photoreceptors, which is advantageous for reducing manufacturing costs.

The charge generation layers 12 and 22 in the electrophotographic photoreceptor according to the present invention may have any conventionally known structure as long as it has photoconductivity. For example, 0, 5 to 20Q mainly composed of A-5i:II deposited by plasma CVD.
Examples include those having a film thickness of about 100 yen, and those further containing Ge, C, etc. In the present invention, such charge injection from the charge generation layer to the charge transport layer can be performed satisfactorily.

In the electrophotographic photoreceptor according to the present invention, a carbon-based film having excellent charge transport ability and high electrical resistance (reciprocal of electrical conductivity) prepared under the conditions described in the following examples is used as the charge transport layer. Since the charge generation layer 12.22
can be made to have a lower resistance than that of conventional electrophotographic photoreceptors. Specifically, for example, lO→0Ωcm
It may be less than that. Therefore, it becomes possible to use materials that have been difficult to use due to their high photoconductivity but low resistance, and extremely high sensitivity can be obtained.

The supports 14 and 24 of the electrophotographic photoreceptor according to the present invention may be made of an insulator or a conductor as long as the mechanical strength as a support is satisfied, but when used repeatedly, at least It is desirable that the sides 14 and 24 in contact with the photosensitive layer are treated to be conductive. Conductive supports include AI, Fe, Ni, stainless steel, Sn, Zn,
Cr, Mo, Ti, Ta, W, Au, A
Metals such as G, Pt, Si, Ge, graphite, etc. can be used. The surface of the conductive support may be coated with a conductive substance other than the support metal for the purpose of improving the adhesion of the photosensitive layer or for other purposes. As the insulating support, in addition to organic polymers such as polyester, polyurethane, polycarbonate, polystyrene, polyamide, and PE, inorganic materials such as glass and ceramics can also be used. The size and shape of the support can be freely selected depending on the intended use of the electrophotographic photoreceptor of the present invention, and any support can be used, including a small card-like support that can be held in the palm of the hand, a cylindrical support, or a belt-like support. It is.

In the case of the electrophotographic photoreceptor shown in FIG.
It is desirable to provide In particular, the charge generation layer 11 is
:H, it is preferable to provide the surface layer 11 in order to improve prevention of image deterioration in a high humidity environment and prevention of image quality deterioration due to the influence of corona discharge products. Various materials can be used for the surface layer 11 as long as it is transparent to some extent in the visible light region and has low electrical conductivity. For example, A-5iC()l formed by plasma CvD etc.
, X), or A-SiN(H,X). Further, a layer mainly composed of carbon that can be used for the charge transport layers 13 and 23 may be used, but in that case, the optical band gap is preferably 2. It is desirable that it be OeV or higher. The electrical conductivity and hydrogen content are not particularly limited as long as they satisfy the characteristics required for the surface layer. Furthermore, the surface layer 11 may contain halogen atoms such as fluorine and chlorine, and hydrogen in addition to C and Si. The halogen atoms may be contained only near the free surface of the surface layer, or may have a concentration gradient from the surface toward the interior.

In the case of the electrophotographic photoreceptor shown in FIG. 2, the charge injection blocking layer 21
is preferably provided between the charge generation layer 22 and the support 24. This makes it possible to further improve charging performance and further prevent defects in image quality. As the charge injection blocking layer 21, A-5i (It, X) doped with impurities formed by plasma CVD or the like can be used. It is preferable that the charge injection blocking layer 21 be doped with p-type when the photoreceptor is used with positive charge, and with n-type when used with negative charge. Group Ⅰ atoms such as B and Al are used to make the p-type, and N is used to make the n-type.

Group V atoms such as P, 8S are suitable as dopants.

Charge transport layers 13 and 23 of the electrophotographic photoreceptor according to the present invention
uses a vapor phase film-forming method as described below, specifically, excitation, ionization, or decomposition of a gas containing a carbon compound using discharge energy, thermal energy, or light energy under the conditions shown in the examples. etc. During this film formation, the carbonaceous film of the present invention can be obtained by hitting the substrate with accelerated electrons, accelerating ions generated along the way with an electric field, or applying a magnetic field to the plasma generation region. Of course, under certain film forming conditions, it is possible to use sputtering using a solid mainly composed of carbon or a carbon compound as a target without using any carbon compound gas.

Although the details of the film formation mechanism are not clear, the production of carbon ions or carbon compound ions or carbon compound radicals, and when hydrogen is used, the amount of hydrogen supplied is sufficient to produce a high-quality carbon film applicable to the present invention. It is important to obtain When hydrogen is used, it is preferable to at least partially radicalize or ionize it in an excitation process before film formation. moreover,
It is also effective to apply a bias voltage to the substrate to bombard the film-forming surface with ions, or to accelerate electrons toward the substrate to excite the carbon compound near the film-forming surface with electrons. In this case, electrons may be supplied by using a heated filament in addition to plasma. Furthermore, even when a bias voltage is not directly applied to the substrate from an external power source, the self-bias generated by applying high frequency to the substrate side can be used instead of grounding the substrate, as in the case of performing RF plasma CVD, for example. It is desirable to do so. The substrate temperature is also an important parameter, and is preferably set at 450°C or higher.

FIG. 3 shows an example of a film forming apparatus suitable for manufacturing the electrophotographic photoreceptor of the present invention.
．． 28.29.3G, 31.32.33.34.62
Valves shown at 63, 66, and 67 are used to control the gas used for film formation. 39.40°4
1, 42.60 is a gas cylinder that holds desired gas such as raw material gas, etching gas, carrier gas, or doping gas, and 61 is a device for vaporizing liquid materials, which can be flowed together with hydrogen gas or argon gas as necessary. It is now possible to do this. 35.36°37, 38.64.6
5 is a mass flow controller. Reference numeral 52 denotes a vacuum chamber, which communicates with the vacuum pump via the main valve 25. The vacuum Nl 52 is provided so that the whole can be water cooled. Reference numerals 45 and 46 are electrodes to which direct current or alternating current voltage can be applied. A sputtering target can be placed on the surface of the electrode 46 if necessary. 54.68 is a guard electrode, which is grounded like the vacuum J152, and can be removed if unnecessary. Reference numeral 53 denotes a substrate, on the surface of which a photosensitive layer is formed. 44 is a base heating heater whose height can be adjusted.
Various shapes such as tantalum, tantalum wire, spiral wound wire, or mesh are used as necessary, and AC power of 50 Hz is usually applied during heating. 43 is a coil wound around the vacuum chamber 52, and a magnetic field is generated by passing a direct current as necessary. Reference numeral 47 is a 13.56 MHz high frequency power supply that can be matched according to the load impedance. 48 is a DC power supply, 50 and 51 are capacitors, and 49 is an inductance coil. 69
．． 70 is a switching circuit for switching the high frequency application sides of the electrodes 45 and 46 up and down.

FIG. 4 shows another example of a film forming apparatus suitable for manufacturing the electrophotographic photoreceptor of the present invention. In this FIG. 4, reference numeral 79.
8G, 81.82.83.84.85.8B, 87
The valves indicated by 88, 89.90, and 91.92 are used to control the gas used for film formation. By selectively using valves 86 and 85, the gas introduction location can be selected. 72, 73, 74, 75° 76 is a gas cylinder that holds desired gas such as source gas, etching gas, carrier gas, or doping gas, and 78 is a device for vaporizing liquid materials, such as hydrogen gas or argon gas as necessary. It is now possible to stream them together. 93.94.95.96°97 and 98 are mass flow controllers. 71 is the vacuum chamber and main valve 1
04 to the vacuum evacuation pump. 107 is a microwave power source, and lθ9 is a microwave waveguide.

108 is a tuner for matching impedances. 110 is a window glass for the microwave input port, which is made of a quartz plate or other material that does not easily absorb microwaves. Reference numeral 99 denotes a partition plate whose installation position can be changed.By adjusting the position of this partition plate 99, the microwaves incident into the vacuum chamber 71 are reflected, and resonance occurs depending on the position. This makes it possible to cause microwaves to be efficiently absorbed into raw material gas, etc.

106 is an electromagnetic coil that can generate a static magnetic field by applying direct current. Reference numeral 100 is a substrate holder that supports the substrate 103. The base 103 has base heaters 101 and 10.
2 makes it possible to heat the base.

The substrate holder 100 is insulated from the ground, and a voltage can be applied by a DC power supply 105. 108 is a guard electrode.

Carbon compounds containing halogen atoms that can be used as raw materials for producing carbon-based membranes according to the present invention include halogen derivatives of alkane hydrocarbons such as methane, ethane, propane, and butane (e.g., cH3ci, C
D3F sudo), mataethylene, propylene, butylene,
Halogen derivatives of alkane hydrocarbons such as amidino,
Further examples include halogen derivatives of alkyne hydrocarbons such as acetylene, pentyne, butyne, and hexyne. Furthermore, benzene, naphthalene, anthracene, toluene,
Xylene or halogen derivatives of aromatic hydrocarbons such as lysine, picoline, quinoline, indole, acridine, phenol, and cresol, alcohols such as methanol, ethanol, propatool, butanol, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, Halogenated derivatives of ketones such as diisobutylketone and diacetyl, halogenated derivatives of aldehydes such as acetaldehyde, propionaldehyde, and butyraldehyde, halogenated derivatives of amines such as methylamine, dimethylamine, trimethylamine, ethylamine, and propylamine, dimethyl ether, Ethers such as methyl ethyl ether, diisopropyl ether, and methyl n-butyl ether or derivatives thereof, and halides of acetic acid derivatives such as methyl acetate and ethyl acetate can also be used. Among these, those that are liquid or solid at room temperature are preferably transported into the reaction chamber by bubbling or other means using a carrier gas such as hydrogen or argon, or are vaporized by heating. Hydrogen, ammonia, etc. may be sent into the reaction chamber together with the above carbon compounds.

Boron compounds such as carbon, substituted borane, -carbon oxide, etc. can be used.

Among these, those that are liquid or solid at the operating temperature ′
using hydrogen, argon, or other carrier gas.
It can be transported to the reaction chamber by bubbling or otherwise, or it can be vaporized by heating.

In addition, when doping atoms of group Ⅰ or group V of the periodic table, BH3, B2H6, PH3, AsH3,
Hydride such as NH3, Al(CH3)3, Ga(
It is preferable to simultaneously feed a gas such as CHa)3 to form a film.

(Example〕 Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Using the apparatus shown in FIG. 3, the electrophotographic photoreceptor shown in FIG. 1 was produced in the following manner.

First, a disc-shaped n-type silicon wafer with an electrical conductivity of about 10-2 Ω-1 cm-1 is used as the base 53, and after removing an oxide film on the surface of the base with a dilute aqueous solution of hydrofluoric acid, this base is used as the upper electrode. It was fixed at 45. Next, the vacuum chamber 52 was sealed, and the pressure was reduced to approximately 2×1O−7 Torr using an evacuation system. Next, 50 Hz alternating current power was applied to the tungsten wire 44 wound thinly to match the circular shape of the base, and the wire 44 was heated to approximately 2500° C. The resulting radiant heat heated the silicon substrate. . After waiting until the back side of the silicon substrate reaches 450°C, lower the wire 44 to about 2000°C to lower the substrate temperature to about 45°C.
It was stabilized at 0°C.

Next, DC power was applied to the electromagnetic coil 43, and the magnitude of the current was controlled so that the magnetic field at the surface of the upper container of the vacuum [52] became 800 Gauss. Furthermore, set the switching circuits 69 and 70 to the A position, and connect the DC power supply 48 to the base side.
I adjusted it to make a V. Then, with the mass flow controller 37.38 squeezed to the maximum, CHF3 cylinder 41
valves 28 and 33, valve 29 of H2 cylinder 42
and 34 were opened. And the flow rate of each gas is 5SC
The mass flow controllers 37 and 38 were set so that CM and 1oss (:CM).At this time, the pressure was 0.
．． 002 Torr.

Next, turn on the power supply 47 to start discharging, and increase the input power to 3.
Adjusted to 50W. 48 hours after the whole reaches a stable state, the discharge power supplies 47 and 48 are turned off, and the valve 28.2 is turned off.
9 was closed to stop the discharge. In this way, a charge transport layer with a thickness of about 8 μm mainly composed of carbon was obtained.

Next, the current of the substrate heating filament 44 was weakened and left as it was, and after waiting for the substrate temperature to drop to a measured value of 250'C, the polarity changeover switch 69 and 7° were set to the B state. Next, the valves 62 and 66 of the SiH4 cylinder 60
Open the valves 29 and 34 of the H2 cylinder 42, and
The mass flow controllers 64 and 38 were adjusted so that iH4 was 105G (:M) and H2 was 90SCCM. Then, the high frequency power supply 47 was turned on, and a
The above charge generation layer consisting of -5i:H was laminated on the charge transport layer.

Following this, the valves 27 and 32 of the C, H, cylinder 40 are opened, and acetylene is added to SiH4 and H2 using the mass flow meter 36, and approximately 10OA A surface layer consisting of A-5i (::H) was laminated.

After all film formation is completed, the valve 27.28.29°3
2, 33, 34, and 30 were closed and the current to the heating filament 44 was cut off to allow the substrate to cool sufficiently, the vacuum was broken and the substrate on which the above-described layers were formed was taken out from the vacuum chamber 52.

In this way, an electrophotographic photoreceptor having the structure shown in FIG. 1 was obtained.

The electrophotographic photoreceptor thus obtained was set in an experimental electrophotographic copying machine and its electrophotographic properties were measured.
It showed good chargeability and photosensitivity.

Subsequently, it was negatively charged, imagewise exposed, and developed with toner, resulting in a high quality image.

Example 2 Except for changing the preparation conditions of the charge transport layer as follows,
An electrophotographic photoreceptor was produced in the same manner as in Example 1.

The substrate bias was -100V, and the substrate temperature was 450°C. Using CH3F and H2 as raw material gases, CH3P at IO5GcM and H2 at 11005 CC in a vacuum chamber 52.
I sent it inside. The filament temperature was 2400°C and the RF power was 300W. A current was passed through the coil 43, and film formation was performed in a magnetic field of 600 Gauss. The pressure during film formation was 0.02 Torr.

When the electrophotographic properties of the electrophotographic photoreceptor thus obtained were measured in the same manner as in Example 1, it showed high charging ability and sensitivity, and when negatively charged, toner images were exposed, and developed. A good image was obtained.

Under the same conditions as above, it was confirmed that only the charge transport layer contained Si wood.

Example 3 An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the conditions for forming the charge transport layer were changed as follows.

The charge transport layer was formed using a mixed gas of CH3F, hydrogen, and ammonia, and the flow rates were IO5CCM for CH3F, 875CCM for hydrogen, and 35CCM for ammonia. Pressure is 0.002 Torr %RF power 350W 1 substrate bias -230V, substrate temperature 550℃, magnetic field 800G
It was called auss.

On the other hand, when the obtained electrophotographic photoreceptor was set in an experimental copying machine in the same manner as in Example 1 and its electrophotographic properties were measured, it showed good charging properties and sensitivity.

Separately, a clear image was obtained by imagewise exposure with positive charging and toner development.

Example 4 An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the conditions for forming the charge transport layer were changed as follows.

A mixed gas of C)I3(:l, hydrogen, and hydrogen fluoride was used to form the charge transport layer.The flow rate was C)13+1;l=20
SC (:M, 77 SCCM of hydrogen, 10 m of hydrogen fluoride
3SCCM dilution gas with o1% hydrogen, RF power 450W, substrate bias Ov, substrate temperature 250℃,
The test was carried out at a pressure of 0 and 0 ITorr.

The electrophotographic photoreceptor thus obtained exhibited good charging properties as in the examples, and a positive charging toner image of good quality was obtained.

Example 5 An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the conditions for forming the charge transport layer were changed as follows.

The charge transport layer was formed using a mixed gas of CH3F and hydrogen, with a flow rate of CH3F of 55C (:M) and hydrogen of 9
5S (:CM). Then, add 1 mol of hydrogen to this.
% diborane was poured in at a rate of 0.55 CCM. Pressure is 0.06 Torr, substrate temperature is 350"C
Film formation was performed at 3RF power of 250 W and substrate bias of -100 V.

The completed electrophotographic photoreceptor exhibited good charging properties as in Example 1, and a toner image of good image quality was obtained with positive charging.

Example 6 The electrophotographic photoreceptor shown in FIG. 2 was produced in the following manner using the apparatus shown in FIG. 3 which had been modified to be able to form a film on a cylindrical substrate.

Using an Al cylindrical base, first apply vacuum JfI52 to approximately 2×1
The vacuum was evacuated to 0' Torr. Next, add 1 base to 23
Heat to 0 °C and add M, H to SiH4 fil05C.
2 flow rate 90SCCM, B2H6 flow rate 0.5SCCM
as 0. A charge injection blocking layer made of P-type A-Si:H containing B at a high density was formed to a thickness of 1000 nm using an RF power of 150 W at ITorr. Next, SiH4 and B
Ihr discharge was continued by setting the flow rate of 2O to 0 and flowing only H2. After that, SiH4 was again flowed at 1O5C (:M) and discharged at a H2 flow rate of 90SCCM, with an A-5 of about 1μ.
A charge generation layer consisting of i:H was formed on the charge injection blocking layer.

After this, the flow of SiH4 and H2 is stopped and 4X 10-
' After reducing the pressure to Torr, a charge transport layer was formed under the following conditions. That is, C, H3P and B2H6 were used and fed into the vacuum chamber 52. c2Hs F flow rate 2
Diborane 0.55C (:M, pressure I Torr) diluted to 1 mol1% with hydrogen was added to this.The RF power was 450W, and the substrate bias was 17%.
0V, and the magnetic field strength was 500 Gauss.

The electrophotographic photoreceptor thus obtained was modified for experimental use.
P75501 (Canon Co., Ltd.) was used for continuous and repeated image formation, and all transferred images had good image quality.

Example 7 Using the apparatus shown in FIG. 4, an electrophotographic photoreceptor having the structure shown in FIG. 1 was produced in the following manner.

As a film forming condition for the charge transport layer, microwave power is 600.
W, a mixed gas of CH3Cl and hydrogen was used as the source gas. The microwave frequency was 2.45 GHz.

CH3Cl flow rate is 55CCM, hydrogen flow rate is 505C
The pressure was set to 0,0007 Torr in CM. The magnetic field is 87
5 Gauss so that electron cyclotron resonance occurs. Under these conditions, adjust the position of the partition wall 99 and create a vacuum! f
When i71 was made to operate as a microwave cavity resonator, plasma was observed blowing out from the opening of the partition wall 99. Substrate temperature is 350℃, substrate bias is 1+50
It was set to V. The thickness of the charge transport layer formed under these conditions was 9
．． It was 3μ.

On top of the charge transport layer created in this way, A
-A charge generation layer of Si:H was created. First, the current to the substrate heating heater 102 was turned off and the temperature of the substrate was waited for to drop to 100°C, and then the current was turned on again to keep it constant at 200°C. Next, SiH4 was converted into IO5CCM.

Flow M of H2 into 50SG and increase the pressure to 2.6x 1O-3
Torr, the magnetic field was set to 875 Gauss, and microwaves were applied. The microwave power was 300W. In this way, a charge generation layer consisting of about 1 gm of A-5t:H was formed on the charge transport layer, and then a C4 flow rate of 7SG was formed.
CM, SiH4 flow rate 3SCCM%H7 flow rate 50SCCM
A surface layer was formed using the above steps, and an electrophotographic photoreceptor having the structure shown in FIG. 1 was obtained.

When this photoreceptor was set in an experimental electrophotographic device and its electrophotographic characteristics were measured, it showed high chargeability and good sensitivity.
When imagewise exposed and developed with negative charge, a good image was obtained.

Example 8 An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the conditions for forming the charge transport layer were changed as follows.

The charge transport layer was formed using CH3Cl and hydrogen gas, with a flow rate of CH3Cl at 55C and hydrogen at 11005M.
CC, 0.5 SCCM of phosphine diluted to 101101!1 with hydrogen, and the pressure was 0.3 Torr.

Substrate temperature 350℃, IIF power 600W% magnetic field 400
The film was formed at Gauss and the substrate bias was -200V.

When the electrophotographic properties of the thus obtained electrophotographic photoreceptor were measured in the same manner as in Example 1, a negatively charged toner image of good quality was obtained.

Example 9 Using the apparatus shown in FIG. 5, an electrophotographic photoreceptor having the structure shown in FIG. 2 was produced in the same manner as in Example 6 except that the following film forming conditions and operations were used.

Using an AI cylindrical substrate, first create a vacuum layer 52 of about 6 x 10'
The vacuum was evacuated to Torr. Next, heat the substrate to 230℃
Heated to SiH4 flow rate 30SCCM%H2 flow rate 180S
CCM, B2H6 flow i 1.5SCCM, 0
．． A charge injection blocking layer made of P-type A-5i:H doped with B at a high concentration was formed to a thickness of 1000 nm using an RF power of 500 W at ITorr. Next, SiH4 and B,
The flow rate of H6 was set to 0, and only H2 was allowed to flow to continue lhr discharge. After that, 30SCCM of SiH4 was poured again, and H
2-current i11805 (:(:M discharge, about 1μ A
A charge generation layer made of -Si:H was formed on the charge injection blocking layer.

After this, the flow of SiH4 and H2 is stopped and 4X 10-
' After reducing the pressure to Torr, a charge transport layer was formed under the following conditions. That is, c, H, F and H2 are sent to the vacuum layer 52, and c, H, F are IO5CCM%.
The H2 was 300 SCCM and the pressure was 0.7 Torr. In addition, the RF power was 650W and the body bias was -111W.
0V, and the magnetic field strength was 600 Gauss.

The electrophotographic photoreceptor thus obtained was positively charged and exhibited good charging properties. This photoreceptor is used in a commercially available copying machine (Canon N
After installing the P7550) in a modified experimental device, image formation was performed, and good initial image quality was obtained. 1
Good image quality was maintained even after a 200,000 copy test.

Embodiment 10 Using the device shown in FIG. 3, the polarity changeover switches 69 and 70 are
An electrophotographic photoreceptor having the structure shown in FIG. 1 was prepared in the same manner as in Example 1 except that the conditions for forming the charge transport layer were changed as follows.

The charge transport layer was formed using CHF3 as a raw material, and the flow rate was 11
005CC, pressure 0.02Torr, RF power 150
W, the substrate temperature was 230° C., and the substrate heating filament 44 was lowered to about 800° C. during film formation. No current is passed through the electromagnetic coil, and no magnetic field is applied near the base.
Ta. The thickness of the charge transport layer formed under these conditions was 18 μm.

Example 11 It was confirmed that the thus obtained electrophotographic photoreceptor having the structure shown in FIG. 1 could be used practically. Using the apparatus shown in FIG. An electrophotographic photoreceptor was produced in the same manner as in Example 1 except for the following.

The charge transport layer was formed using CH3 (:l) and hydrogen gas, and the flow rate was CH3 (:l: 50SCCM, hydrogen at 505C).
(:M, pressure 0.03 Torr, RF power 450W
, substrate bias OV, and substrate temperature were 450 at the start of film formation.
℃, and then the current of the substrate heating heater 44 was cut off during film formation. The voltage of the DC bias power supply 48 was set to Ov, and the polarity changeover switches 69 and 70 were set to the A state when forming the charge transport layer. No magnetic field was used. The thickness of the charge transport layer formed under these conditions was 8JAgI.

It was confirmed that the electrophotographic photoreceptor thus obtained could be used practically.

Embodiment 12 Using the device shown in FIG. 3, the polarity changeover switches 69 and 70 are
An electrophotographic photoreceptor having the structure shown in FIG. 1 was prepared in the same manner as in Example 1 except that the conditions for forming the charge transport layer were changed as follows.

The charge transport layer was formed using 114 H, CI and hydrogen gas as raw materials, with flow rates of H, IO5 CCM, and hydrogen 90 SC (:
M, pressure 5 Torr, RF power 250W, substrate temperature 2
00°C, and the substrate heating filament 44 was heated to 80°C during film formation.
The temperature was lowered to about 0°C. No current was passed through the electromagnetic coil, and no magnetic field was applied near the substrate. The thickness of the charge transport layer obtained under these conditions was 18 JAj.

It was confirmed that the thus obtained electrophotographic photoreceptor having the structure shown in FIG. 1 could be used for.

Example 13 Using the apparatus shown in FIG. 3, an electrophotographic photoreceptor was produced in the same manner as in Example 1, except that the charge transport layer was formed under the following conditions.

The charge transport layer was formed using C2Hj Fa and hydrogen gas, and the flow rate was 1205 CCM of fine GFa5 SCCM and 1205 CCM of hydrogen.
, the pressure was 0.03 Torr, the RF power was 450 W, the substrate bias was OV, the substrate temperature was 450° C. at the start of film formation, and the current of the substrate heating heater 44 was turned off during film formation. The voltage of the DC bias power supply 48 is set to Ov,
The polarity changeover switches 69 and 70 are set to A when forming the charge transport layer.
I made it into a state. No magnetic field was used. The thickness of the charge transport layer formed under these conditions was 8 μm.

It was confirmed that the electrophotographic photoreceptor thus obtained could be used practically.

〔Effect of the invention〕

As explained above, the effects brought about by the present invention include those listed below.

l) It has become possible to provide an electrophotographic photoreceptor that has high charging ability and can form images with a small charging current and a small amount of exposure energy.

2) It has become possible to provide an electrophotographic photoreceptor capable of high-speed image formation.

3) It has become possible to provide an electrophotographic photoreceptor that can easily produce high-quality images with high density, clear halftones, and high resolution.

4) It has become possible to provide an electrophotographic photoreceptor that can maintain stable images against changes in the usage environment such as temperature and humidity.

5) An electrophotographic photoreceptor that is less susceptible to adhesion of corona discharge products and paper dust during repeated use, and that can be used while maintaining stable images over long periods of time without scratching the surface. It became possible to provide.

6) An electrophotographic photoreceptor that does not undergo chemical changes, deterioration, crystallization, or other changes in the photosensitive layer, and can withstand long-term storage in adverse environments and reproduce the same good image quality as before storage. It became possible to provide.

7) It is completely harmless even if it comes into contact with the human body during the manufacturing process or when handled in an office, etc., and part of the photosensitive layer may be scraped and mixed into the developer, and it will be included in the toner image on the copy. It is completely safe even if it comes into contact with the human body, and if necessary, it can be disposed of with some garbage after use without any safety problems, and there are no special precautions when using it at home. It has become possible to provide an electrophotographic photoreceptor that can be used safely and does not emit toxic gases even if it is burned together with other materials in an emergency such as a fire, and is therefore completely safe in all respects. .

8) It is possible to manufacture products without using harmful raw materials during production, or with an extremely small amount of harmful raw materials compared to conventional methods, and for this reason, it is possible to manufacture products using hazardous material abatement equipment and equipment that must be installed in manufacturing equipment. It has now become possible to provide an electrophotographic photoreceptor that can significantly reduce the cost required for other manufacturing safety measures.

9) It has become possible to provide a low-cost electrophotographic photoreceptor that can use readily available and inexpensive raw materials for manufacturing.

10) It does not require complicated processes such as mixing and dispersing non-uniform materials or controlling particle size distribution, and also allows for preparation of coating liquids, viscosity control during coating, and treatment of interlayer contamination and solvent exhaust that occur during multilayer structures. It has become possible to provide an electrophotographic photoreceptor that can be manufactured by a simplified process that does not require , and can be manufactured using manufacturing equipment that is easy to maintain.

11) To provide an electrophotographic photoreceptor that does not generate fine particles due to non-formation of fine powder during manufacturing or peeling off of a film adhered to the inside of a manufacturing container, and can stably obtain a defect-free and uniform photosensitive layer for a long period of time. became possible.

[Brief explanation of the drawing]

1 and 2 are schematic structural cross-sectional views showing examples of embodiments of the electrophotographic photoreceptor according to the present invention, and FIGS. 1 is a schematic diagram showing an example of a device that can be used. FIG. 14 and 24 are supports, 13.23 is a charge transport layer, 12.
22 is a charge generation layer, 11 is a surface layer, 21 is a charge injection blocking layer, 52.71 is a vacuum chamber for film formation, 47 is a high frequency power source, 107 is a microwave power source, 45.48 is an electrode,
100 is a substrate holder, and 43 and 106 are electromagnetic coils.

Claims (4)

[Claims] (1) A method for producing an electrophotographic photoreceptor having a photosensitive layer in which a charge generation layer and a charge transport layer are laminated on a support, the charge transport layer being formed of a carbon compound containing a halogen atom and a reducing agent. 1. A method for producing an electrophotographic photoreceptor, comprising the step of forming a film containing carbon as a main raw material. (2) The electrophotographic photoreceptor according to claim 1, wherein the carbon-based film contains at least one or more atoms selected from the group consisting of hydrogen, nitrogen, and oxygen. manufacturing method. (3) The method for producing an electrophotographic photoreceptor according to claim 1, wherein the carbon-based film contains atoms belonging to Group III of the periodic table at a concentration of 5 at % or less. (4) The method for manufacturing an electrophotographic photoreceptor according to claim 1, wherein the carbon-based film contains atoms belonging to Group V of the periodic table at a concentration of 5 at % or less.