JPS6161102B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
The present invention relates to an electrophotographic image forming member used to form an image using electromagnetic waves such as.

[Conventional technology]

Conventionally, photoconductive materials constituting the photoconductive layer of electrophotographic image forming members include inorganic photoconductive materials such as Se, CdS, and ZnO, poly-N-vinylcarbazole (PVK), and trinitrofluorenone (TNF). Organic photoconductive materials (OPCs) are commonly used.

However, regarding electrophotographic photoreceptors using these photoconductive materials, there are still various issues that need to be resolved, and the conditions may be relaxed to a certain extent, depending on individual circumstances. The reality is that any suitable electrophotographic imaging member is used.

For example, in an electrophotographic image forming member that uses Se as a photoconductive layer forming material, if Se alone is used, the spectral sensitivity range is narrow when using light in the visible light range, so Te or As is added to the spectral sensitivity range. It is planned to expand.

However, although electrophotographic image forming members having such Se-based photoconductive layers containing Te and As certainly improve the spectral sensitivity range, optical fatigue increases, making it difficult to print the same original. Continuously copying may cause a decrease in the image density of the copied image or background stains (fogging), and if you continue copying other documents, the image of the previous document may be copied as an afterimage (ghost development). It has the following disadvantages.

However, since Se, especially As and Te, are extremely harmful substances to the human body, it is necessary to devise ways to use manufacturing equipment that does not come into contact with the human body during manufacturing. The capital investment is significantly large. Furthermore, if the photoconductive layer is exposed even after manufacturing, the surface of the photoconductive layer will be directly rubbed during cleaning and other treatments, and a portion of it will be scraped off, causing the developer to They may get mixed into the machine, be scattered inside the copying machine, or be mixed into the copied images, causing them to come into contact with the human body.

Furthermore, when the surface of a Se-based photoconductive layer is continuously and repeatedly exposed to corona discharge many times, crystallization or oxidation occurs near the surface of the layer, leading to deterioration of the electrical properties of the photoconductive layer. There are many cases. Or again,
If the surface of the photoconductive layer is exposed, when a liquid developer is used to visualize (develop) the electrostatic latent image,
Since it comes into contact with the solvent, it is required to have excellent solvent resistance (resistance to liquid development), but in this regard, it cannot be said that the Se-based photoconductive layer necessarily satisfies the conditions. hard.

Separately, Se-based photoconductive layers are usually formed by vacuum evaporation, which requires significant capital investment in equipment and is difficult to reproduce a photoconductive layer with desired photoconductive properties. In order to obtain good performance, it is necessary to strictly adjust various manufacturing parameters such as evaporation temperature, evaporation substrate temperature, degree of vacuum, evaporation rate, and cooling rate.

In addition, the Se-based photoconductive layer has a high dark resistance as a photoconductive layer of an electrophotographic image forming member.
Although it is formed in an amorphous state, since crystallization of Se occurs at an extremely low temperature of approximately 65°C, it may be exposed to ambient temperature during handling after manufacture or during use or other components during the image forming process. It also has a drawback in terms of heat resistance, in that it is highly influenced by frictional heat caused by rubbing and causes crystallization development, which tends to lead to a decrease in dark resistance.

On the other hand, electrophotographic imaging members that use ZnO, CdS, etc. as photoconductive layer constituent materials have a photoconductive layer in which particles of the photoconductive material such as ZnO or CdS are uniformly dispersed in a suitable resin binder. It is formed by This electrophotographic image forming member having a so-called binder-based photoconductive layer is advantageous in manufacturing compared to an electrophotographic image forming member having an Se-based photoconductive layer, and has a relatively low manufacturing cost. can be measured. That is, the binder-based photoconductive layer is made of ZnO or CdS.
It is formed by simply applying a coating solution prepared by kneading particles of and an appropriate resin binder using an appropriate solvent onto an appropriate substrate by a coating method such as a doctor blade method or a dipping method, and then solidifying the coating solution. Therefore, compared to an electrophotographic image forming member having a Se-based photoconductive layer, it is not necessary to invest as much capital in manufacturing equipment, and the manufacturing method itself is simple and easy.

However, the binder-based photoconductive layer is basically a two-component system consisting of a photoconductive material and a resin binder, and the photoconductive material particles are uniformly dispersed in the resin binder. Due to the specific characteristics of the photoconductive layer, there are many parameters that determine the electrical and photoconductive properties as well as the physical and chemical properties of the photoconductive layer. It is not possible to form a conductive layer with good reproducibility,
This method has the disadvantage that it leads to a decrease in yield and lacks mass productivity.

In addition, because the binder-based photoconductive layer is a dispersed system, the entire layer is porous, and as a result, it is highly dependent on humidity, and when used in a humid atmosphere, the electrical properties deteriorate, making it difficult to maintain high quality. In many cases, it becomes impossible to obtain a duplicate image.

Furthermore, the porous nature of the photoconductive layer causes developer to enter the layer during development, which not only reduces mold releasability and cleaning properties but also makes it unusable. When a developer is used, the developer permeates into the layer together with the carrier solvent due to capillary action, which makes the above point more significant, so it is necessary to cover the surface of the photoconductive layer with a surface coating layer. .

However, even with this improvement by providing a surface coating layer, the surface of the photoconductive layer is uneven due to the porous nature of the photoconductive layer, so the interface is not uniform and the adhesion between the photoconductive layer and the surface coating layer is poor. Another disadvantage is that it is difficult to obtain good electrical contact.

In addition, when using CdS, since CdS itself has an effect on the human body, care must be taken during manufacturing and use to prevent it from coming into contact with the human body or scattering into the surrounding environment. There is a need to.

When using ZnO, there is almost no effect on the human body, but ZnO binder-based photoconductive layers have drawbacks such as low photosensitivity, narrow spectral sensitivity range, significant optical fatigue, and slow photoresponsiveness. have. or,
In electrophotographic image forming members that use organic photoelectric materials such as PVK and TNF, which have been attracting attention recently,
Manufacturing advantages and flexibility in that a photoconductive layer can be formed simply by forming a coating film of an organic photoconductive material such as PVK or THF on a suitable support such as polyethylene terephthalate whose surface has been conductively treated. However, on the other hand, it has low photosensitivity, for example, when the light used for image formation is in the visible light range, the spectral sensitivity range is narrow and It has drawbacks such as being biased toward the short wavelength side, so it can only be used in a very limited range.

As described above, electrophotographic image forming members using photoconductive materials, which have been pointed out as materials for forming the photoconductive layer of electrophotographic image forming members, have both advantages and disadvantages, so there are some difficulties in manufacturing them. In order to meet the requirements and usage conditions, the current situation is that the manufacturing and usage conditions are relaxed to some extent, and an appropriate electrophotographic image forming member suitable for each use is selected and put into practical use. .

Therefore, there is a need for a third material for forming the photoconductive layer of an electrophotographic image forming member, which can provide an excellent electrophotographic image forming member that solves the above-mentioned problems.

Among such materials that have recently been viewed as promising is amorphous silicon (hereinafter abbreviated as A-Si).

A-Si films, which are still in the early stages of development, show a variety of electrical and optical properties because their structure is influenced by the manufacturing method and manufacturing conditions, which poses a major problem in terms of reproducibility. I was holding it. For example, in the early stages, A-Si films formed by vacuum evaporation or sputtering methods contained a large amount of defects such as voids, which greatly affected their electrical and optical properties. It did not receive much attention as a research material for fundamental physical properties, and no research and development was conducted for its application. However, since it was thought that p and n control was impossible in amorphous, in 1976
At the beginning of 2017, it was reported that a p-n junction could be realized for the first time using amorphous metal (Applied Physics
Letter; Vol. 28, No. 2, 15 January 1976), there has been a great deal of interest, and since then, in addition to the ability to obtain p-n junctions by doping the impurities mentioned above, crystalline silicon (c- Since luminescence, which is very weak in A-Si (abbreviated as Si), can be observed with high efficiency, research and development efforts have been focused mainly on its application to solar cells.

In this way, the A-Si films that have been reported so far have been developed for use in solar cells, so their electrical and optical properties are
The reality is that it cannot be used as a photoconductive layer in an electrophotographic imaging member. In other words, solar cells convert solar energy into electric current and extract it.
In order to not only have a good signal-to-noise ratio but also to extract a large current efficiently, the resistance of the A-Si film must be low to some extent, but if the resistance is too low, the photosensitivity will decrease and the signal-to-noise ratio will deteriorate. As one of its characteristics, a resistance of about 10 ⁵ to ^{10 8} Ω·cm is required.

However, the resistance (dark resistance) of the A-Si film having this level of resistance (dark resistance) is too low to be used as a photoconductive layer of an electrophotographic image forming member. As it is, it cannot be used at all by applying currently known electrophotographic methods.
Furthermore, photoconductive layer forming materials for electrophotographic image forming members are required to have bright resistance (resistance when irradiated with light) that is about 2 to 4 orders of magnitude smaller than dark resistance, but this has not been reported in the past. The conventional A-Si film has a photoconductive layer of about 2 digits at most, so in this respect too, the conventional A-Si film could not provide a photoconductive layer that fully satisfies the characteristics.

Also, in another report regarding A-Si film,
For example, it has been shown that an A-Si film with a dark resistance of 10 ¹⁰ Ωcm has a similar bright resistance and a poor signal-to-noise ratio. The A-Si film could not serve as a photoconductive layer for an electrophotographic imaging member.

[Purpose and structure]

This was made in view of the above points of the present invention, and
-Results of intensive and comprehensive research on Si from the perspective of its application to electrophotographic image forming membersA-
By laminating the Si layer and the layer of the organic compound described in detail below, the resulting electrophotographic imaging member is not only usable for practical use, but also has good performance when compared with conventional electrophotographic imaging members. It is based on the fact that it was found to be superior in most respects.

The present invention makes it possible to easily create a closed system for manufacturing equipment during manufacturing, thereby avoiding adverse effects on the human body. Furthermore, it is non-polluting with no impact on the natural environment, has stable electrophotographic characteristics at all times, and is an all-environment type with almost no restrictions on usage environments.
The main object of the present invention is to provide an electrophotographic image forming member that is extremely resistant to light fatigue and does not cause deterioration even after repeated use.

Another object of the present invention is to provide an electrophotographic image forming member that can easily produce high-quality images with high density, clear halftones, and high resolution.

Another object of the present invention is to provide an electrophotographic image forming member that has high photosensitivity, has a spectral sensitivity range that covers substantially the entire visible light range, and has fast photoresponsiveness.

Still another object of the present invention is to provide an electrophotographic image forming member with fewer restrictions on the time required for development after electrostatic image formation and the time required for development.

An intended object of the present invention is to provide a layer containing amorphous silicon containing 10 to 40 atom % of hydrogen, which generates a movable carrier by electromagnetic wave excitation, and which is used as an image forming member for electrophotography. This is achieved by providing a structure in which the carriers generated in the layer are injected and a layer made of an organic compound for effectively transporting the injected carriers. .

The most typical structural example of the electrophotographic image forming member of the present invention is shown in FIGS. 1 and 2.

The electrophotographic imaging member 1 shown in FIG.
a support 2 for an imaging member applied to the implementation of electrophotography; an A-Si layer 3 in which a movable carrier is generated by electromagnetic wave excitation; It consists of a layer 4 of an organic compound for efficient injection and effective transport of carriers, the layer 4 having a free surface 5.

In the present invention, the A-Si layer 3 is the image forming member 1.
For the electromagnetic wave irradiation step, which is one step in the process of forming an electrostatic image on the surface of 40atomic
% of amorphous silicon.

In the present invention, since the A-Si layer 3 has the above-mentioned function, it is possible to substantially obtain sufficient contrast depending on the direction in which the image forming member 1 is irradiated with electromagnetic waves. The support is designed so that a carrier sufficient to form an electrostatic image can be generated in the A-Si layer 3, that is, so that the electromagnetic waves can sufficiently reach the A-Si layer 3. It is necessary to form either layer 2 or layer 4.

That is, for example, in FIG. 1, when irradiating electromagnetic waves from the layer 4 side, the layer 4 is the A-Si layer 3.
It is necessary to select the material and determine the layer thickness so that an amount of electromagnetic waves that generates a sufficient amount of carrier can pass through and reach the A-Si layer 3. , when irradiating electromagnetic waves from the support 2 side, the layer 4 when the support 2 is under the above conditions.
It is necessary to select the material and determine the layer thickness.

Further, in the image forming member 1 shown in FIG. 1, an A-Si based layer 3 is formed on the support 2, and
Although the layer 4 is formed on the -Si-based layer 3, the order of the layer structure does not necessarily limit the present invention. A layer structure order having a free surface may also be used. With this layer configuration, when electromagnetic waves are irradiated from the A-Si layer 3 side, the organic compound layer 4 and the support 2 will have a sufficient carrier in the A-Si layer 3 as described above. A large amount of electromagnetic waves are generated in the A-Si layer 3.
There is no need to make it possible to reach . On the other hand, when electromagnetic waves are irradiated from the support 2 side, the support 2 and the layer 4 have the A-Si layer 3 as described above.
In this case, it is necessary to select the material and determine the layer thickness so that an amount of electromagnetic waves that generates a sufficient amount of carrier can reach the A-Si layer.

The support 2 may be electrically conductive or electrically insulating. Examples of the conductive support include stainless steel, Al, Cr, Mo, Au, Ir, Nb, Ta,
Examples include metals such as V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose triacetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, its surface is conductive treated with In ₂ O ₃ or SnO ₂ , or if it is a synthetic resin film such as polyester film, it is treated with Al, Ag,
Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V,
Vacuum evaporation, electron beam evaporation with metals such as Ti and Pt,
The surface is made conductive by sputtering or by laminating with the metal. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined depending on the need. In the case of continuous high-speed copying, an endless belt or a cylindrical shape is used. It is desirable to do so. The thickness of the support is appropriately determined so as to form a desired electrophotographic image forming member, but if flexibility is required as an electrophotographic image forming member, the thickness of the support may be determined as appropriate. It is made as thin as possible within a range that allows for sufficient functionality. However, in such a case, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc.

The A-Si layer 3 is formed on the support 2 by a glow discharge method, a sputtering method, an ion implantation method, or the like. These manufacturing methods are appropriately selected and adopted depending on factors such as manufacturing conditions, equipment capital investment load, manufacturing scale, and electrophotographic characteristics desired for the electrophotographic image forming member to be manufactured. , the introduction of impurities into the A-Si layer to control the properties is relatively easy to control to produce an imaging member with the desired electrophotographic properties, replacing group or group impurities. The glow discharge method is preferably employed because of its advantages such as being able to be introduced using a mold. Furthermore, in the present invention, the A-Si layer may be formed by using a glow discharge method and a sputtering method in the same apparatus system.

The A-Si layer 3 is controlled to contain hydrogen (H) so that the electrophotographic image forming member targeted by the present invention can be obtained. The inclusion of T in the A-Si-based layer 3 means that SiH ₄ and Si ₂ H ₆ are present in the device system when forming the layer 3.
It is also possible to introduce such compounds in the form of compounds such as, decompose them by a method such as thermal decomposition or glow discharge decomposition, and incorporate them into the A-Si layer 3 as the layer grows. Alternatively, doping may be performed by ion implantation.

According to the findings of the present inventors, the content of H in the A-Si layer 3 influences whether the formed electrophotographic image forming member can be sufficiently applied in practice. It has been found that this is one of the major factors and is extremely important.

In order for the electrophotographic imaging member to be formed in the present invention to be fully applicable to practical applications, A-Si
The amount of H contained in the system layer is usually 10~
It is desirable that it be 40 atomic%, preferably 15 to 30 atomic%. The theoretical basis for why the H content in the A-Si layer is limited to the above numerical range has not yet been clarified and remains in the realm of speculation. However, from numerous experimental results, it has been found that, in some cases, when the H content is outside the above numerical range, for example, the produced electrophotographic imaging member has extremely low sensitivity to irradiated electromagnetic waves. In some cases, the sensitivity is almost not observed, the increase in carrier due to electromagnetic wave irradiation is small, the dark resistance of the A-Si layer is extremely low, etc., and the H content is within the above numerical range. It is confirmed that this is a necessary condition. In order to contain H in the A-Si based layer 3, for example, A-Si
When forming a system layer, hydrides such as SiH ₄ and Si ₂ H ₆ are used as the starting material for forming A-Si, so hydrides such as SiH ₄ and Si ₂ H ₆ are used under the production conditions described below. When the A-Si layer is formed by decomposition below,
H is automatically contained in the layer, but in order to incorporate H into the layer more efficiently, when forming the A-Si layer, it is necessary to introduce H ₂ gas into the glow discharge system. It would be good to introduce it.

When using the sputtering method, H ₂ gas is introduced when sputtering is performed using Si as a target in an inert gas such as Ar or a mixed gas atmosphere based on these gases, or SiH ₄ ,
A silicon hydride gas such as Si ₂ H ₆ or a gas such as B ₂ H ₆ or PH ₃ which also serves as impurity doping may be introduced.

In order to control the amount of H contained in the A-Si layer, the temperature of the support and/or the amount of the starting material used to contain H introduced into the apparatus system may be controlled. Furthermore, one method is to heat the layer at a temperature below the crystallization temperature after forming the A-Si layer.

In the present invention, the thickness of the A-Si layer 3 is usually set to 0.1 μm or more in order to ensure a practically sufficient sensitivity to the irradiated electromagnetic waves.

On the other hand, as an upper limit, the layer thickness normally known for photoconductive layers in the field of electrophotography is good enough, but it is possible to shorten the time required to manufacture the A-Si layer and From the viewpoint of reducing costs, it is desirable that the thickness is usually 10μ or less, preferably 7μ or less.

As the impurity to be doped in the A-Si layer, in order to make the A-Si layer p-type, elements of group A of the periodic table, such as B, Al, Ga, In, Tl, etc., are preferable. In the case of n-type, elements of group A of the periodic table, such as N, P,
Preferred examples include As, Sb, Bi, and the like.
Since the amount of these impurities contained in the A-Si layer is on the order of ppm, there is no need to pay attention to their pollution, but it is preferable to use impurities that are as non-polluting as possible. From this point of view, B, As, P, Sb, etc. are optimal, taking into account the electrical and optical properties of the A-Si layer to be formed.

The amount of impurity doped into the A-Si layer is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities in group A of the periodic table, it is usually 10 ^-6 ~10 ^-3 atomic%, preferably 10 ^-5 ~
10 ^-4 atomic%, in the case of impurities of group A of the periodic table, usually 10 ^-8 to 10 ^-5 atomic%, preferably 10 ^-8 to 10 -5 atomic%.
It is desirable to set it to 10 ^-7 atomic%.

The method of doping these impurities into the A-Si layer differs depending on the manufacturing method adopted when forming the A-Si layer. This will be explained in detail in the examples.

In the present invention, the layer 4 made of an organic compound is
The carriers generated in the A-Si layer 3 are efficiently injected and the layer 4 is a layer for effectively transporting the injected carriers, so the layer 4 effectively transports the injected carriers. The material is selected so as to be provided on the A-Si layer 3 so as to form a good contact condition such that carrier injection from the A-Si layer 3 can be carried out smoothly.

In order to form the layer 4 that satisfies these conditions, the forming material must have a hole mobility relative to an electron mobility when the A-Si layer 3 is n-type. A relatively large one is selected, and in the case where the A-Si layer 3 is p-type, one whose electron mobility is relatively large compared to the hole mobility is selected and used. Many organic compounds are suitable as such materials because many of them have film-forming properties, adhesive properties, and required resistance.

However, on the already formed organic compound layer 4,
In the case of forming an A-Si type layer, as will be clear from the following explanation, a heat-resistant organic compound must be selected as the organic compound forming the layer 4.

Most of these organic polymer compounds can be dissolved in a suitable solvent and formed by a conventional coating method such as a doctor blade method or dipping method.

Substances with relatively high hole mobility that can be effectively used in the present invention include PVK, carbazole, N-ethylcarbazole, N-isopropylcarbazole, N-phenylcarbazole, tetraphenylpyrene, and 1-methylpyrene. , perylene, chrysene, anthracene, tetracene, tetraphene, 2-phenylnaphthalene, azapyrene, fluorene, fluorenone, 1-ethylpyrene, acetylpyrene, 2,3-benzochrysene,
3,4-benzopyrene, 1,4-bromopyrene,
Examples include phenylindole, polyvinylpyrene, polyvinyltetracene, polyvinylperylene, polyvinyltetraphene, and polyacrylonitrile. Materials with relatively high electron mobility include PVK: TNF, (monomer molar ratio 1:
Examples of 1) include tetranitrofluorenone, dinitroanthracene, dinitroacridene, tetracyanophyllene, dinitroanthraquinone, and the like.

The image forming member 1 shown in FIG. 1 has a layer structure in which an A-Si layer 3 is laminated on a support 2 and a layer 4 made of an organic compound is laminated on the layer 3. Further, a layer 4 is provided between the support 2 and the A-Si layer 3.
Another layer similar to that may be provided. In this case, when the layer 4 has a relatively high electron mobility, the layer provided between the support 2 and the A-Si layer 3 is a layer with a relatively high hole mobility. When the layer 4 has a relatively high hole mobility, it is a layer with a relatively high electron mobility.

The layer thickness of the layer 4 made of an organic compound is determined according to the characteristics and A required for the layer 4 in order to achieve the object of the present invention.
The thickness is determined as appropriate in relation to the -Si-based layer, but it is usually 5 to 80μ, preferably 10 to 50μ.

A layer 4 made of an organic compound or an A-Si based layer 3, such as the electrophotographic imaging member shown in FIG. In the image forming member to be processed, a carrier is injected from the support 2 side during the charging process during electrostatic image formation between the support 2 and the layer provided on the support 2. It is even more preferable to provide a barrier layer that acts to prevent this. Materials for forming a barrier layer with this function include:
An appropriate one is selected and used depending on the type of support 2 selected and the electrical characteristics of the layer formed on the support 2. Examples of such barrier layer forming materials include inorganic compounds such as Al ₂ O ₃ , SiO, and SiO ₂ , organic compounds such as polyethylene, polycarbonate, polyurethane, and parylene, Au, Ir,
Examples include metals such as Pt, Rh, Pd, and Mo.

The electrophotographic imaging member 6 shown in FIG.
Except for having a surface coating layer 10 having a free surface 11, the support 7, the layer 8A made of an organic compound, and the Si-based layer 9 are not essentially different from the image forming member 1 shown in FIG. . However, the characteristics required of the surface coating layer 10 differ depending on the electrophotographic process to which it is applied. In other words, Special Public Interest Publication 1977-
If you apply the electrophotographic process described in Publications No. 23910 and No. 43-24748,
The surface coating layer 10 is required to be electrically insulating, have sufficient ability to retain static charge when subjected to charging treatment, and have a certain thickness or more. If this process is applied, it is desirable that the potential of the bright area after electrostatic image formation be very small, so the thickness of the surface coating layer 10 is required to be very thin. In addition to satisfying the desired electrical properties, the surface coating layer 10 should not have any adverse chemical or physical effects on the A-Si layer 9 and should not have any electrical contact with the A-Si layer 9. contactability and adhesion, as well as moisture resistance,
It is formed taking into consideration wear resistance, cleanability, etc.

Typical materials effectively used for forming the surface coating layer 10 include polyethylene terephthalate, polycarbonate, polypropylene, polyvinyl chloride, polyvinylidene chloride,
Polyvinyl alcohol, polystyrene, polyamide, polytetrafluoroethylene, polytrifluorochloroethylene, polyvinyl fluoride, polyvinylidene fluoride, hexafluoropropylene-tetrafluoroethylene copolymer, trifluoroethylene-vinylidene fluoride copolymer , synthetic resins such as polybutene, polyvinyl butyral, and polyurethane, and cellulose derivatives such as diacetate and triacetate. These synthetic resins or cellulose derivatives may be formed into a film and laminated onto the A-Si layer 9, or a coating liquid may be formed and applied onto the A-Si layer 9. Apply,
A film may be formed.

The layer thickness of the surface coating layer 10 is appropriately determined depending on the desired characteristics and the material used, but is usually about 0.5 to 0.7 μm. In particular, when the surface coating layer 10 is required to function as the above-mentioned protective layer, the thickness is usually 10μ or less, and on the other hand, when the surface coating layer 10 is required to function as an electrically insulating layer, the thickness is usually set to 10μ or less. In this case, it is considered to be 10μ or more. However, the layer thickness value that differentiates the protective layer from the electrically insulating layer varies depending on the materials used, the applied electrophotographic process, and the structure of the electrophotographic imaging member designed. The value of 10μ is not absolute.

Next, when manufacturing the electrophotographic photoreceptor of the present invention, the case where the A-Si layer is manufactured by the glow discharge method and the sputtering method will be explained. FIG. 3 is a schematic explanatory diagram of a glow discharge vacuum deposition apparatus for producing an A-Si based layer by a capacitance type (capacitive coupling type) glow discharge method.

12 is a glow discharge deposition tank, and inside thereof,
A substrate (supporting body) 13 for forming an A-Si layer is fixed to a fixing member 14, and a heater 15 for heating the substrate 13 is installed at the lower end of the substrate 13. Capacitance type electrodes 17, 17' connected to a high frequency power source 16 are wound around the upper part of the deposition tank 12, and when the high frequency power source 16 is turned on, high frequency waves are applied to the electrodes 17, 17'. The voltage is applied so that a glow discharge is generated within the deposition tank 12.

A gas introduction pipe is connected to the upper end of the deposition tank 12, so that the gas in each cylinder is introduced into the deposition tank 12 from the gas cylinders 18, 19, and 20 when necessary. Reference numerals 21, 22 and 23 are flow meters for detecting the flow rate of gas, 24, 25 and 26 are flow control valves, 27, 28 and 29 are valves, and 30 is an auxiliary valve. .

Further, the lower end of the deposition tank 12 is connected to an exhaust device (not shown) via a main valve 31. 32 is pulp for breaking the vacuum in the deposition tank 12.

Using the glow discharge device shown in FIG.
To form an A-Si layer with desired characteristics on the substrate 13, first, the substrate 13 that has been subjected to a predetermined cleaning treatment is placed with the cleaned side facing upward, or the substrate 13 on which a layer made of an organic compound has been previously provided is placed. It is fixed to the fixing member 14 provided with the layer.

To clean the surface of the substrate 13, a commonly used method, for example, a chemical treatment method using an alkali or an acid, is employed. Alternatively, after being cleaned to some extent, it may be placed at a predetermined position in the accumulation tank 12, and glow discharge treatment may be performed before forming a dark resistance layer thereon. In this case, since the process from cleaning the substrate 13 to forming the A-Si layer can be performed in the same system, it is possible to avoid dirt and impurities from adhering to the cleaned substrate surface. After fixing the substrate 13 to the fixing member 14, the main valve 31 is fully opened to exhaust the air in the deposition tank 12, and the vacuum level is
Set it to about 10 ^-5 torr.

After the interior of the deposition tank 12 reaches a predetermined degree of vacuum, the heater 15 is ignited to heat the substrate 13, and once the substrate 13 reaches a predetermined temperature, it is maintained at that temperature.

Next, the auxiliary valve 30 is fully opened, and then the valve 24 of the gas cylinder 18 and the valve 25 of the gas cylinder 19 are fully opened. The gas cylinder 18 is, for example, Ar.
The gas cylinder 19 is for diluting gas such as gas.
It is for raw material gas for forming A-Si, and for example, SiH ₄ , Si ₂ H ₆ , Si ₄ H ₁₀ or a mixture thereof is stored. The cylinder 20 is used for raw material gas to generate impurities to be introduced into the A-Si layer as needed, and stores PH ₃ , P ₂ H ₄ , B ₂ H ₆ and the like.

Thereafter, the flow rate control valves 24 and 25 of the gas cylinders 18 and 19 are gradually opened while watching the flow meters 21 and 22, and a dilution gas such as Ar gas and SiH ₄ gas is introduced into the deposition tank 12. Introduce raw material gas for Si formation. At this time Ar
A diluent gas such as gas is not necessarily required, and only the source gas such as SiH ₄ gas may be introduced. When introducing Ar gas mixed with a raw material gas for A-Si formation such as SiH ₄ gas, the quantitative ratio is determined according to desire, but in normal cases, the raw material gas for dilution gas is introduced. Gas is considered to be 10Vol% or more. Note that He is used as a diluent gas instead of Ar gas.
A rare gas such as gas may also be used.

At the point when gas is introduced into the deposition tank 12 from the cylinders 18 and 19, the main valve 32 is adjusted to a predetermined degree of vacuum, usually at the raw material gas pressure for forming A-Si. Keep at 10 ^-2 to 3 torr. Next, when a predetermined frequency (usually 0.2 to 30 MHz frequency) is applied by the high frequency power source 16 to the capacitance type electrodes 17 and 17' wound outside the deposition tank 12, a glow discharge is caused inside the deposition tank 12. For example, SiH ₄ gas is decomposed and Si is deposited on the substrate 13 to form an A-Si layer.

When introducing impurities into the A-Si layer to be formed, a gas for impurity generation is supplied from the cylinder 20 to the A-Si layer.
- It may be introduced into the deposition tank 12 at the time of forming the Si-based layer. In this case, by appropriately adjusting the flow rate control valve 26, the flow rate from the cylinder 20 to the deposition tank 12 can be adjusted.
Since it is possible to appropriately control the amount introduced into
In addition to being able to arbitrarily control the amount of impurities introduced into the A-Si layer to be formed,
It is also possible to easily change the amount of impurities in the thickness direction of the system layer.

In the glow discharge deposition apparatus shown in Fig. 3, an RF (radio feguency) capacitance type glow discharge method is adopted.
Glow discharge methods such as RF inductance type and DC bipolar type are also employed in the present invention. Further, electrodes 17 and 17' for glow discharge are connected to the deposition tank 12.
It may be provided outside the deposition tank 12, or it may be provided inside the deposition tank 12.

In a capacitance type glow discharge device such as the device shown in FIG. 3 according to the present invention, in order to obtain an effective glow discharge, the current density must be set at 0.1 to 10
A/cm ² is best, and in order to obtain sufficient power, it is usually 100 to 5000V, preferably 300 to 5000V.
It is best to adjust the voltage to .

Since the characteristics of the formed A-Si layer largely depend on the substrate temperature during growth, it is preferable to strictly control it. In the present invention, the substrate temperature is usually
By setting the temperature in the range of 50 to 350°C, preferably 100 to 200°C, an A-Si layer having effective properties is formed. Further, the substrate temperature can be changed continuously or intermittently during the formation of the A-Si layer to obtain desired characteristics.

Figure 4 shows A-Si produced by sputtering method.
FIG. 2 is a schematic explanatory diagram showing one of the apparatuses for manufacturing the system layer.

Reference numeral 33 is a vacuum deposition tank, inside which is a conductive substrate 34 for forming an A-Si layer, which is electrically insulated from the deposition tank 33, similar to that explained in FIG. It is fixed to a fixed member 35 and placed at a predetermined position. A heater 36 for heating the substrate 34 is disposed below the substrate 34, and a polycrystalline or single crystal silicon target 37 is disposed above the substrate 34 at a predetermined interval and facing the substrate 34.

A high frequency voltage is applied by a high frequency power source 38 between the fixing member 35 on which the substrate 34 is installed and the silicone target 37. Further, in the deposition tank 33, cylinders 39 and 40 are connected to valves 41 and 42, and flow meters 43 and 4, respectively.
4. Flow rate adjustment valves 45, 46, auxiliary valve 47
, and gas is introduced into the deposition tank 33 from the cylinders 39 and 40 when necessary.

Now, using the apparatus shown in FIG.
To form the Si-based layer, first, as shown by arrow B, the air in the deposition tank 33 is evacuated through the main valve 48 using a suitable exhaust device to achieve a predetermined degree of vacuum. Next, the heater 36 is ignited and the board 3
4 to a predetermined temperature. When forming an A-Si layer by sputtering method, this substrate 3
The heating temperature in step 4 is usually 50 to 350°C, preferably 100 to 350°C.
It is said to be 200℃. This substrate temperature influences the growth rate of the A-Si layer, the layer structure, the presence or absence of voids, etc.
Since this is one element that determines the physical properties of the formed A-Si layer, sufficient control is required. Further, the substrate temperature may be kept constant during the formation of the A-Si layer, or may be raised, lowered, or raised or lowered as the A-Si layer grows. For example, in the early stages of forming an A-Si layer, the substrate temperature is maintained at a relatively low temperature _T1 , and once the layer has grown to a certain extent, the substrate temperature is increased to a temperature _T2 higher than _T1 while forming the layer. However, at the end of layer formation, the temperature T ₃ is lower than T ₂ again.
The A-Si layer can be formed by, for example, lowering the substrate temperature. By doing this, A-
The electrical and optical properties of the Si-based layer can be changed continuously in the layer thickness direction.

In addition, A-Si has a layer growth rate of, for example,
Since it is slower than Se, etc., when the layer thickness is increased, the A-Si formed at the beginning of the layer formation (A-Si near the substrate side) loses the characteristics of the initial stage of the layer formation until the end of the layer formation. Because there is a strong possibility that it may change,
In order to form an A-Si layer having uniform properties in the thickness direction of the layer, it is desirable to form the layer while increasing the substrate temperature from the start of layer formation to the end of layer formation.

Next, after detecting that the substrate 34 has been heated to a predetermined temperature, the main valve 48 and the auxiliary valve 4
7. Fully open valves 41 and 42. Next, while adjusting the main valve 48 and the flow control valve 46, H ₂ gas is introduced into the deposition tank 33 from the cylinder 40 until it reaches a predetermined degree of vacuum, and is maintained at that degree of vacuum.

Subsequently, the flow rate control valve 45 is opened, and atmospheric gas such as Ar gas is introduced from the cylinder 39 into the deposition tank 33 until a predetermined vacuum level is reached, and the vacuum level is maintained. In this case, the flow rates of the H ₂ gas and atmospheric gas into the deposition tank 33 are set to achieve the desired physical properties.
- It is appropriately determined so that a Si-based layer is formed. For example, the pressure of the mixed gas of atmospheric gas and H ₂ gas in the deposition tank 33 is a degree of vacuum, usually 10 ^-3 to 10 ^-1 Torr,
It is preferably 5×10 ⁻³ to 3×10 ⁻² Torr. still,
Ar gas can also be replaced with rare gas such as He gas.

Atmospheric gas such as Ar gas and
After the H ₂ gas is introduced, the fixing member 35 on which the substrate 34 is installed and the silicon target 37 are heated at a predetermined frequency and voltage by the high frequency power supply 38.
During this time, a high frequency voltage is applied to cause a discharge, and the generated Ar ions sputter the silicon target, forming an A-Si layer on the substrate 34.

In the explanation of FIG. 4, a sputtering method using high frequency discharge is used, but a sputtering method using direct current discharge may also be adopted. In the sputtering method using high frequency application, the frequency is usually 0.2 to 30 MHz, preferably 5 to 30 MHz in the case of the present invention.
20MHz, and the discharge current density is usually 0.1 to 10
mA/cm ² , preferably 1 to 5 mA/cm ² . Also, in order to obtain sufficient power, usually
The voltage is preferably adjusted to 100-5000V, preferably 300-5000V.

The growth rate of the A-Si layer when manufacturing an A-Si layer by the sputtering method is mainly determined by the substrate temperature and discharge conditions. This is one of the factors.
The growth rate of the A-Si layer to achieve the purpose of the present invention is usually 0.5 to 100 Å/sec, preferably 1 to 100 Å/sec.
It is desirable to set it to 50 Å/sec.

In the sputtering method, as in the glow discharge method, A is formed by doping with impurities.
-Si-based layer can be adjusted to n-type or p-type. The method of introducing impurities is the same in the sputtering method as in the glow discharge method; for example, PH ₃ ,
Substances such as P ₂ H ₄ and B ₂ H ₆ are introduced in a gaseous state into the deposition tank 33 during the formation of the A-Si layer to dope P or B as an impurity into the A-Si layer. In addition to this, impurities may be introduced into the formed A-Si layer by ion implantation. In this case, the extremely thin surface layer portion of the A-Si layer can be easily controlled to have desired characteristics.

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

Example 1 Using the apparatus shown in FIG. 3, an electrophotographic image forming member of the present invention was prepared in the following manner, and an image was formed by performing an image forming process.

1 mm thick, surface treated with 1% NaOH solution, thoroughly washed with water and dried to clean the surface.
Prepare an aluminum substrate with a size of 10 cm x 5 cm, and place the heater 15 at a predetermined position on the fixing member 14 at a predetermined position in the glow discharge deposition tank 12 by about 10 cm.
It was firmly fixed at a certain distance.

Next, the main valve 31 is fully opened to open the deposition tank 1.
The air in the chamber was evacuated to create a vacuum of approximately 5×10 ⁻⁵ Torr. Thereafter, the heater 15 was ignited to uniformly heat the aluminum substrate to 150° C., and this temperature was maintained. After that, the auxiliary valve 30 is fully opened, and then the valve 27 of the cylinder 18 and the valve 1 of the cylinder 18 are opened.
After fully opening the valve 28 of 9, the flow rate adjustment valve 2
4 and 25 gradually, and put Ar from cylinder 18.
Gas is transferred from cylinder 19 to SiH ₄ gas in deposition tank 12.
introduced within. At this time, the main valve 31 was adjusted so that the degree of vacuum in the deposition tank 12 was maintained at about 0.75 Torr.

Subsequently, the switch of the high frequency power supply 16 was turned on and a high frequency voltage of 13.56 MHz was applied between the electrodes 17 and 17' to generate a glow discharge and form an A-Si layer on the aluminum substrate 13. The glow discharge power at this time was 5W. Also, at this time A-Si
The growth rate of the system layer was about 4 Å/sec, and the layer was formed for about 20 minutes, and 0.5 Å/sec was formed on the aluminum substrate 13.
A μ-thick A-Si layer was formed. In this way A-
After the layer formation is completed, the main valve 31, valves 27, 28, flow rate adjustment valves 24, 25, and auxiliary valve 30 are closed, and the valve 32 is opened instead to vacuum the substrate on which the Si-based layer is formed. I tore it up and took it outside.

Next, a coating prepared by dissolving PVK in toluene was applied onto the A-Si based layer by a doctor blade method. Next, this was left in an atmosphere at 80° C. for about 2 hours to evaporate the toluene. The thickness of the PVK film after drying was approximately 15μ. The image forming member thus obtained was subjected to an image forming process as described below.

First, in the dark, a negative corona discharge was applied to the image forming surface with a power supply voltage of 5500V, and then a
Image exposure was performed from the image forming surface at an exposure amount of lux.sec to form an electrostatic image, and the electrostatic image was developed with positively charged toner by a cascade method to transfer and fix it onto a transfer paper. At this time, although the processing time from charging to completion of development was approximately several seconds, a highly clear transferred image with high resolution was obtained. Also, furthermore,
Even when the processing time exceeded 10 seconds, almost no decrease in the contrast of the transferred image was observed.

Example 2 Thickness was deposited on an aluminum substrate in the same manner as in Example 1, except that glow discharge was performed in a state where B ₂ H ₆ gas was mixed with SiH ₄ gas at a ratio of 0.01%.
A 0.5μ thick A-Si layer was obtained. A coating solution obtained by dissolving PVK:TNF in a mixture of equal amounts of toluene and cyclohexanone was applied onto this A-Si layer using a doctor blade method, and then the mixture was heated to 80°C in order to evaporate the solvent. It was left in the atmosphere for about 2 hours.
The layer thickness of PVK:TNF after drying was approximately 20μ.
This is positively corona charged with a power supply voltage of 6000V in the dark, and then image exposure is performed from the image forming surface with an exposure amount of 15 lux.sec to form an electrostatic image.
When this electrostatic image was developed with negatively charged toner by a cascade method and transferred and fixed onto a transfer paper, an extremely clear image with high resolution was obtained. On the other hand, when image processing was carried out in the same manner using negative corona discharge for charging and positively charged toner for development, the resulting transferred image had low contrast.

Example 3 Surface treated with 1% NaOH solution, thoroughly washed with water and dried to clean the surface, 1 mm thick.
An aluminum substrate with a size of 10 cm x 5 cm was prepared, and a coating solution obtained by dissolving polyacrylonitrile in dimethylformamide was applied onto it using a doctor blade method. Next, this was left in an atmosphere of about 80°C for about 1 hour to evaporate dimethylformamide, and then left in an atmosphere of about 250°C for about 2 hours for the purpose of heat treatment. The thickness of the polyacrylonitrile layer after drying was 20μ. An A-Si layer was formed on the polyacrylonitrile layer thus obtained by sputtering as described below using the apparatus shown in FIG.

First, a substrate 34 having a polyacrylonitrile layer
was firmly fixed at a predetermined position of a fixing member 35 in a predetermined position in the deposition tank 33, with the polyacrylonitrile layer on the upper surface and about 10 cm apart from the heater 36. In addition, about 8.5 cm from the board 34 is placed on the top of the board 34.
A polycrystalline silicon target 37 with a purity of 5 nines was fixed at the position. Next, the main valve 48 is opened to exhaust the air in the deposition tank 33, and about 1×
The degree of vacuum was set at 10 ^-6 Torr. Then the heater 36
ignite to uniformly heat the board 34 and bring the temperature to about
The temperature was set at 150°C, and this temperature was maintained thereafter.

After that, the valve 47 is fully opened, and then the valve 41 of the cylinder 39 is fully opened, and then the flow rate adjustment valve 4 is fully opened.
5, gradually open Ar gas from the cylinder 39 while adjusting it with the main valve 48 until the vacuum level is 5.5×.
It was introduced into the deposition tank 33 at a pressure of 10 ^-4 Torr. Next, after fully opening the valve 42 of the cylinder 40, while watching the flow meter 44, gradually open the flow control valve 46' until the degree of vacuum is 5×10 ^-3 Torr.
H ₂ gas was introduced into the deposition tank 33 in such a manner that

After that, the switch of the high frequency power supply 38 is turned on to connect the substrate 34 and the polycrystalline silicon target 37.
A high frequency voltage of 13.56 MHz and 1 KV was applied to cause discharge, and the formation of an A-Si layer on the polyacrylonitrile layer was started. The growth rate of the A-Si layer at this time was controlled at about 2 Å/sec, continued for about 40 minutes, and was about 0.5 μ
An A-Si based layer was formed. When the image forming member thus produced was subjected to image processing in the same manner as in Example 2, a transferred image with good line quality was obtained. On the other hand, in the case of negative charging, the contrast of the obtained transferred image was significantly lower than that in the case of positive charging.

Example 4 After forming a polyacrylonitrile layer (layer thickness 15 μm) and an A-Si layer (layer thickness 0.5 μm) on an Al substrate in the same manner as in Example 3, Example 2 PVK:TNF was applied in the same manner as (layer thickness
15μ).

When the image forming member thus produced was subjected to image processing in the same manner as in Example 2, a high quality transferred image was obtained in the case of positive charging. On the other hand, in the case of negative charging, the contrast of the transferred image obtained was significantly lower than that in the case of positive charging.

Example 5 Sheet of polyethylene terephthalate (thickness
An image forming member was obtained in the same manner as in Example 1 except that the substrate was made of aluminum (100μ) thinned. Image processing was performed in the same manner as in Example 1, except that image exposure was performed from the substrate side using this. The resulting transferred image was of high quality.

Example 6 A polyacrylonitrile layer (thickness 15μ) and an A-Si layer (layer thickness) were deposited on an Al substrate in the same manner as in Example 3.
After forming a layer of 0.5μ), a polycarbonate resin was coated on the A-Si layer to a thickness of 15μ after drying to form a transparent insulating layer to obtain an image forming member. A negative corona discharge is applied to the surface of the insulating layer of the image forming member at a charging voltage of 6000V as a primary charge, and after about 5 seconds, a positive corona discharge is performed at a charging voltage of 5500V as a secondary charge at the same time with an exposure dose of 20 lux.sec. Image exposure was performed, and then the entire surface of the image forming member was uniformly irradiated to form an electrostatic image. When this was developed with positively charged toner using the cascade method and transferred and fixed onto transfer paper, a clear image with high resolution was obtained.

[Brief explanation of the drawing]

1 and 2 are schematic cross-sectional views showing a part of the structure of the electrophotographic image forming member of the present invention, and FIGS. 3 and 4 show the manufacture of the electrophotographic image forming member of the present invention. FIG. 1, 6... Image forming member for electrophotography, 2, 7...
Support, 3, 9... A-Si layer, 4, 8... Organic compound layer, 5, 11... Free surface, 10... Surface coating layer, 12, 33... Vacuum deposition tank, 13, 34
... Board, 14, 35 ... Fixing member, 15, 36
...Heater, 16,38...High frequency power supply, 17,
17'...Capacitance type electrode, 18,1
9,20,39,40...Gas cylinder, 21,2
2, 23, 43, 44...Crowmeter, 2
4, 25, 26, 45, 46...flow control valve, 27, 28, 29, 41, 42... valve,
30, 47...auxiliary valve, 31,48...main valve, 32...leak valve.

Claims (1)

[Claims] 1. A layer containing amorphous silicon that generates movable carriers by electromagnetic wave excitation and contains 10 to 40 atomic percent hydrogen, and the carriers generated in the layer are injected, 1. An electrophotographic image forming member comprising: a layer made of an organic compound transported therein; 2. The electrophotographic image forming member according to claim 1, wherein the organic compound layer has a relatively high electron mobility. 3. The electrophotographic image forming member according to claim 1, wherein the organic compound layer has a relatively high hole mobility. 4. The electrophotographic image forming member according to claim 1, further comprising a barrier layer on the opposite side of the layer containing amorphous silicon to the side where the organic compound layer is provided. 5 The layer containing amorphous silicon has p
The electrophotographic image forming member according to claim 1, which contains a type or n-type impurity.