JPS6035059B2 - Electrophotographic photoreceptor and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor and a method for manufacturing the same.

Conventionally, photoconductive materials constituting the photoconductive layer of electrophotographic photoreceptors include inorganic photoconductive materials such as Se, CdS, and Zn○, and poly-N-vinylcarbazole (PVK) and trinitrofluorenone (TNF). Organic photoconductive material (OPC)
is commonly used.

However, in electrophotographic photoreceptors using these photoconductive materials, there are still some issues that can be solved.
The reality is that appropriate electrophotographic photoreceptors are used depending on individual circumstances, with some degree of relaxation of conditions.

For example, an electrophotographic photoreceptor using Se as a material for forming a photoconductive layer has a narrow spectral sensitivity range when Se alone is used, so attempts are being made to widen the spectral sensitivity range by adding Te or As. However, although such an electrophotographic photoreceptor having a Se-based photoconductive layer containing Te or As does improve the spectral sensitivity range, optical fatigue increases, so the same original cannot be printed continuously. Repeated copying may cause a decrease in the image density of the copied image and background stains (fogging), and if you subsequently copy another original, the image of the previous original will be copied as an afterimage (ghost development), etc. have.

However, since Se, especially As and Te, are extremely harmful substances to the human body, it is necessary 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 after manufacturing, that is, even if the product is a product, when it undergoes cleaning or other treatments, the surface of the photoconductive layer will be directly smudged, and a portion of it will be scraped off. This creates an opportunity for the particles to come into contact with the human body, such as being mixed into the developer, scattered into the copying machine, or mixed into the copied image. Also, if the surface of the photoconductive layer is exposed,
When a liquid developer is used to visualize (develop) a static latent image, the solvent resistance (liquid development resistance) is required due to contact with the solvent.
It is required to be excellent at.

In addition, when the surface of the Se-based photoconductive layer is continuously exposed to corona discharge many times over, crystallization or oxidation occurs near the surface of the layer, resulting in deterioration of the electrical properties of the photoconductive layer. There are many cases.

For these reasons, it is difficult to say that the Se-based photoconductive layer is necessarily satisfactory.

In order to improve these points, the surface of the Se-based photoconductive layer was
It has been proposed to cover it with a surface coating layer called a so-called protective layer, an electrically insulating layer, or the like.

However, with regard to these improvements, there must be sufficient solutions in terms of adhesion between the photoconductive layer and the surface coating layer, electrical contactability, and electrical properties and surface properties required of the surface coating layer. The reality is that it is difficult to say that this will be achieved.

In addition, since the Se-based photoconductive layer is usually formed by vacuum deposition, the equipment for that purpose requires a huge amount of cost.

In order to obtain a photoconductive layer with desired photoconductive properties with good reproducibility, it is necessary to strictly adjust various manufacturing parameters such as deposition temperature, deposition substrate temperature, degree of vacuum, deposition rate, and cooling rate. . Furthermore, since the surface coating layer is formed by pasting a film-like material on the surface of the photoconductive layer via an adhesive or by applying a surface coating layer forming material, the photoconductive layer It is necessary to install equipment for this purpose separately from the equipment for forming the film, which further increases the capital investment. Furthermore, since the Se-based photoconductive layer must have high-order resistance as a photoconductive layer of an electrophotographic photoreceptor, it is formed in an amorphous state.
Since Se crystallization occurs at an extremely low temperature of about 650C, it is subject to environmental temperature during handling after manufacturing, ambient temperature during use, and frictional heat due to sliding with other materials during the image forming process. It also has a drawback in terms of heat resistance, in that it is susceptible to crystallization, which tends to cause a decrease in floor resistance.

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

This electrophotographic photoreceptor having a so-called binder-based photoconductive layer can be manufactured more advantageously than an electrophotographic photoreceptor having an Se-based photoconductive layer, and therefore, manufacturing costs can be relatively reduced. That is, the binder-based photoconductive layer has Z
A coating solution prepared by kneading particles such as n0 or CdS and an appropriate resin binder using an appropriate solvent is applied onto an appropriate substrate.
It can be formed by simply applying it using a coating method such as the doctor blade method or dipping method and then allowing it to solidify.
Compared to an electrophotographic photoreceptor having a Se-based photoconductive layer, it does not require a large investment in manufacturing equipment, and the manufacturing method itself is simple and easy. However, the binder-based light guide layer is basically a two-component system consisting of a photoconductive material and a resin binder, and is formed by uniformly dispersing photoconductive material particles 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 has the disadvantage that it cannot be formed with good reproducibility, resulting in a decrease in yield and lack of mass productivity.

In addition, because the binder-based photoconductive layer is a dispersion system,
The entire layer is porous, and therefore has a significant temperature dependence, and when used in a humid atmosphere, the electrical characteristics deteriorate, often making it impossible to obtain high-quality copied images.

Furthermore, the porous nature of the photoconductive layer causes developer to enter the layer during development, which not only reduces patternability and cleanability but also makes it unusable. When a developer is used, the developer permeates into the layer together with its carrier and solvent due to the promotion of capillary action, making the above point significant. It is necessary to cover the surface 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 Zn○ is used, there is almost no effect on the human body, but the Zn○ binder-based photoconductive layer has low photosensitivity.
It has drawbacks such as a narrow spectral sensitivity range, significant photofatigue, and slow photoresponsiveness. Also, PVK has been attracting attention recently.
For electrophotographic photoreceptors that use organic photoconductive materials such as PVK and TNF, a coating film of organic photoconductive materials such as PVK and TNF is formed on a suitable support such as polyethylene terephthalate whose surface has been subjected to conductive treatment. This method has the advantage in manufacturing that a photoconductive layer can be formed and fired by simply applying the method, and that an electrophotographic photoreceptor with excellent flexibility can be manufactured. It lacks corona ion resistance and cleaning properties, and has drawbacks such as low photosensitivity and a narrow spectral sensitivity range that is biased toward short wavelengths, so its use has been limited to an extremely limited range. .

However, some of these organic photoconductive materials are suspected of being addictive, and there is no guarantee that they are completely harmless to the human body. In this way, electrophotographic photoreceptors using photoconductive materials, which have traditionally been pointed out as materials for forming the photoconductive layer of electrophotographic photoreceptors, have both advantages and disadvantages, so manufacturing and usage conditions are relaxed to some extent. The reality is that each electrophotographic photoreceptor is selected and put to practical use in a manner suitable for each purpose.

The purpose of the present invention was completed in consideration of the above-mentioned points, and the purpose of the present invention is to have no adverse effects on the human body, other living things, or the surrounding environment when handled and used. It has excellent resistance to pollution, heat and humidity, stable electrophotographic properties at all times, is suitable for all environments with almost no restrictions on usage environments, and has excellent resistance to light fatigue and corona ion.Repeated use. An object of the present invention is to provide an electrophotographic photoreceptor that does not cause any deterioration phenomenon even when the electrophotographic photoreceptor is used, and a method for efficiently manufacturing the electrophotographic photoreceptor, which allows an apparatus to be easily converted into a closed system and does not cause pollution problems. be.

Another object of the present invention is to provide an electrophotographic photoreceptor that can easily obtain high-quality images with high density, clear halftones, and high resolution, and a method for manufacturing the same. Still another object of the present invention is to have high photosensitivity, a wide range of spectral sensitivity covering almost all visible light, fast photoresponsiveness, and good abrasion resistance, cleaning properties, and solvent resistance. The purpose of the present invention is to provide an excellent electrophotographic photoreceptor and a method for manufacturing the same.

The intended object of the present invention is achieved by forming the photoconductive layer primarily of amorphous silicon (hereinafter abbreviated as a-Si).

In the early stages of development, a-Si films showed a variety of electrical and optical properties because their structure was influenced by the manufacturing method and manufacturing conditions, and there were major problems in terms of reproducibility. Ta.

For example, in the early stages, a-Si films formed by vacuum evaporation or sputtering methods contained a large number of defects such as voids, which greatly affected their electrical and optical properties. However, it did not receive much attention as a research material for fundamental physical properties, and no research and development efforts were conducted for its application. However, in the early 1976's, it was reported that P'n junction could be realized for the first time in a-Si (App. ter；Vo
So28, No. 2, 15 January and 1976), a great deal of interest has been gathered, and since then, in addition to the fact that p-n junctions can be obtained by doping with the impurities mentioned above, crystalline silicon (abbreviated as c-Si) has From the viewpoint that extremely weak luminescence can be observed with high efficiency in an a-Si film, research and development efforts have been directed primarily toward applications in solar cells (photovoltaics), as seen in U.S. Pat. No. 4,064,521, for example. It is in operation. The US patent discloses a solar cell in which an a-Si body obtained by glow discharge in silane is laminated on a substrate, and thereon is a metal layer and an anti-reflection layer containing an electrode. The U.S. patent also states that the presence of hydrogen in the a-Si body is thought to be advantageous for good electronic properties, but there is no further disclosure regarding this fact. It is not something that has been materialized as such. As described above, since the a-Si films that have been reported so far were developed for use in solar cells, their electrical and optical properties are not suitable for photoconductivity of electrophotographic photoreceptors. The reality is that it cannot be used as a layer.

In other words, solar cells convert solar energy into current and extract it, so in order to have a good signal-to-noise ratio and extract current efficiently, the resistance of the a-Si film must be low. If it is too cold, the photosensitivity will decrease and the S/N ratio will deteriorate, so one of its characteristics is resistance of 1 to 1.
A degree of pi○/c is required. However, the a-Si film with this level of resistance (scale resistance: resistance at the floor) is too low to be used as a photoconductive layer of an electrophotographic photoreceptor, and is currently not suitable for use as a photoconductive layer of an electrophotographic photoreceptor. , it cannot be used at all by applying known electrophotographic methods.

In addition, the material for forming the photoconductive layer of an electrophotographic photoreceptor is required to have a bright resistance (resistance when irradiated with light) that is about 2 to 4 orders of magnitude smaller than the dark resistance. -S
In this respect, the conventional a-S; film could not provide a photoconductive layer that fully satisfies the characteristics. Also, apart from this, the a-Si
Reports on membranes show that increasing the solar resistance decreases the photosensitivity; for example, when the 8-tone resistance increases,
It has been shown that the i-film exhibits similar photoresistance values, but in this respect as well, the conventional a-Si film could not serve as the photoconductive layer of an electrophotographic photoreceptor. .

In addition to the above requirements, the photoconductive layer of an electrophotographic photoreceptor also has requirements such as electrostatic properties, corona ion resistance, solvent resistance, light fatigue resistance, moisture resistance, heat resistance, abrasion resistance, and cleanability. must satisfy.

There are several documents reporting on a-Si, but
There is nothing in any of them that suggests a photoconductive layer of an electrophotographic photoreceptor that satisfies the various requirements mentioned above.

For example, Jom ship l of Photographic
ScienceVol. 25, No. 3, pp. 12
7-28 (N Sasayino J Sarae 1977), a method for producing a-Sj by glow discharge is reported, but there is no specific disclosure of the production method or the resulting a-Si, and it is simply It is merely stated that the resulting a-Si can be a photoconductive material with characteristic density states and transport properties.

Also, SolidStatesCommunication
ons Vol. 23, pp. 155-158 (197
7) contains hydrogenated a-Si prepared by RF sputtering method.
However, the content is based on such a-S
In this study, we investigated the properties of hydrogenated a-Si, which was produced by sputtering, and suggested the possibility of using it as a solar cell material. Therefore, we can only speculate that the internal resistance of the photovoltaic cell will be very high, and in the conclusion of the report, it is stated that ``However, the detailed behavior of the photoresponse as a function of hydrogen introduction is unclear in the Si-day state during transport and recombination.'' raises new questions about the role of

It is also clear that the varying atomic arrangements and structures of the materials, ranging from H-compensated Si to Si-day alloys, need to be carefully considered. Until this is done systematically, the conclusions drawn from tests such as those described here should be considered as preliminary to the new perspectives they suggest. The photoconductive layer of the electrophotographic photoreceptor mentioned above is not mentioned at all. As a result of comprehensive research and study on a-Si from the viewpoint of its application to the photoconductive layer of an electrophotographic photoreceptor, the present invention has discovered that if a-Si is a specific a-Si that can be classified as a-Si, Not only can it be used satisfactorily as a material for forming the photoconductive layer of photographic photoreceptors, but it is also extremely superior in most respects to the material for forming the photoconductive layer of conventional electrophotographic photoreceptors. This is what I completed based on what I saw and what I came up with.

The most typical structural example of the electrophotographic photoreceptor of the present invention is shown in FIGS. 1 and 2. The electrophotographic photoreceptor 1 shown in FIG. 1 includes a support 2, a photoconductive layer 3 mainly made of a-Si, and
The photoconductive layer 3 has a free surface 4 which serves as an image forming surface.
have. The support 2 may be either electrically conductive or electrically insulating.

Examples of the conductive support include stainless steel, A, and C.
r, M〇, Au, lr, Nb, Ta, V, Ti, Pt,
Examples include metals such as Pd and alloys thereof. Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose triacetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide;
Glass, ceramic, paper, etc. are commonly used. It is desirable that at least one surface of these electrically insulating supports is electrically conductive treated. For example, if it is glass, its surface is conductive treated with ln203, Sn02, etc., or if it is a synthetic resin film such as polyester film, it is vacuum evaporated with metal such as Al, Ag, Pb, Zn, Ni, Au, etc. or laminated with the metal, and the surface thereof is subjected to conductive treatment. 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, but in the case of continuous high-speed copying, it may be an endless belt or a cylinder. is desirable.
The thickness of the support is appropriately determined so as to form the desired electrophotographic photoreceptor, but if the electrophotographic photoreceptor requires maneuverability, the thickness of the support may be sufficiently determined. It is made as thin as possible within the specified range. However, in such a case, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is usually set to be 10 degrees or more. a-S
The i-based photoconductive 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 selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, manufacturing scale, and electrophotographic characteristics desired for the electrophotographic photoreceptor to be manufactured. It is relatively easy to control to produce an electrophotographic photoreceptor with specific characteristics.In order to control the characteristics, it is possible to introduce impurities into the a-Si layer using substitutional type M group or V group impurities. The glow discharge method is preferably used because of its advantages such as ease of use. Furthermore, in the present invention, it is an extremely effective method to form the a-Si layer by using both the glow discharge method and the sputtering method in the same system. The resistance of the a-Si photoconductive layer 3 is controlled, for example, by doping, so that the resistance thereof satisfies the value required for the photoconductive layer of the exposure photosensitive member.

Doping of the a-Si-based photoconductive layer 3 is carried out by introducing compounds such as SiH4, Si2, etc. into the device system in the form of SiH4, Si2, etc., or by thermal decomposition and glow discharge when forming the photoconductive layer 3. These compounds or compounds may be decomposed by a method such as decomposition and doped into the a-Si layer as the layer grows, or they may be doped by an ion implantation method. good. According to the findings of the present inventors, a-Si
The amount of doping into the photoconductive layer 3 is determined by the amount of a formed
It has been found that the -Si layer is one of the major factors that determines whether it can be applied as a photoconductive layer of an electrophotographic photoreceptor and is extremely important.

In the present invention, in order for the a-Sj layer to be formed to be sufficiently applicable as a photoconductive layer of an electrophotographic photoreceptor, a-Si
The amount of doping into the layer is typically 10-40
The atomic % is preferably 15 to 3 atomic %.

Regarding the amount of doping into the a-Sj layer, based on numerous experimental results, when it is outside the above numerical range, for example,
As a photoconductive layer of an electrophotographic photoreceptor, phenomena such as the floor resistance being too low, the photosensitivity being extremely low or, in some cases, almost no photosensitivity being observed, and the increase in carrier density due to light irradiation being small, have been observed. It was confirmed that it was necessary for the doping amount to be within the above numerical range. a
- In order to dope the Si layer, for example, when forming the a-Si layer by the glow discharge method, the a-S
Since the starting material for forming j is a hydride such as Si ratio, Si2 day 6, etc., when the hydride such as Si ratio, Si2 day 6, etc. is decomposed and an a-Si layer is formed, the mark is automatically However, in order to more efficiently dope the a-Si layer, it is sufficient to introduce a gas into the system for performing glow discharge when forming the a-Si layer.

When using the sputtering method, S is processed in an atmosphere of an inert gas such as Ar or a mixed gas based on these gases.
When sputtering is performed using i as a target, a gas is introduced, or a borohydride gas such as Si or Si, or it is also doped with impurities.
It is sufficient to introduce a gas such as PH3.

To control the amount of doping into the a-Si layer,
The temperature of the deposition substrate and/or the amount of starting material used to dope the device introduced into the system may be controlled.

Furthermore, after forming the a-Si layer, the layer may be exposed to an activated hydrogen atmosphere. Further, at this time, one method is to heat the a-Si layer below the crystallization temperature. a-
As mentioned earlier, the Si layer can be made intrinsic by doping with impurities during manufacturing, and its conductivity can be controlled, so it is effective when forming an electrostatic image on the electrophotographic photoreceptor. It has the advantage that the polarity of charging can be arbitrarily selected.

This advantage is that in the case of a conventional, for example, Se-based photoconductive layer, depending on the manufacturing conditions such as substrate temperature, type of impurity, and doping amount when forming the layer, it is either P type or It is possible to form an intrinsic type (i type), and also P
This method is much more convenient than the need to strictly control the substrate temperature even when forming a mold.

The impurities doped into the a-Si layer include a-
In order to make the Si layer P-type, suitable elements are those of the mth group A of the periodic table, such as B, A, Ga, ln, T-so, etc., and in order to make the Si layer n-type, , Group V A of the periodic table
Suitable elements include N, P, As, Sb, Bi, and the like. Since the amount of these impurities contained in the a-Si layer is on the order of ppm, it is not necessary to pay as much attention to their pollution properties as the main materials constituting the photoconductive layer. It is preferable to use From this point of view, considering the electrical and optical properties of the a-Si photoconductive layer to be formed, for example, B
, false, P, Sb, etc. are optimal. The amount of impurity doped into the a-Sj layer is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities in group m of the periodic table A, it is usually 10-6. ~10-3 atomic%
, preferably mic% of 10-5 to 10-4a, and in the case of impurities of group V A of the periodic table, usually 10-8 to 10-5
atomic%, preferably 10-8 to 10-? atom
It is desirable to set it as ic%. These impurity a-Si
The method of doping into the layer varies depending on the manufacturing method employed when forming the a-Si layer, and will be specifically explained in detail in the following description or examples.
An electrophotographic photoreceptor such as the electrophotographic photoreceptor shown in FIG. In the photoreceptor, there is a layer between the a-Si photoconductive layer 3 and the support 2 that functions to prevent injection of carrier from the support 2 side during charging processing during electrostatic image formation. More preferably, a barrier layer is provided. As a material for forming a barrier layer having such a function, an appropriate material is selected and used depending on the type of support selected and the electrical characteristics of the a-Si photoconductive layer to be formed. Ru. Examples of such barrier layer forming materials include Au, lr, Pt, Rh, Pd, Mo
For example, when the barrier layer forming material is Au, suitable supports include A and the like. The layer thickness of the a-Si photoconductive layer is determined as appropriate depending on the desired electrophotographic properties and usage conditions, such as whether or not maneuverability is required. In some cases, 5 to 80 French, preferably 10 to 70, most preferably 10 to 70 French.
It is desirable that there be 50 Buddhas.

In an electrophotographic photoreceptor having a layered structure in which the surface of the a-Si photoconductive layer is exposed as shown in FIG. 1, the refractive index of the a-Si film is relatively large at about 3.35. Compared to conventional photoconductive layers, light reflection is more likely to occur on the surface of the photoconductive layer during exposure, and therefore the proportion of the amount of light absorbed by the photoconductive layer decreases, increasing the light loss rate. In order to reduce this optical loss rate as much as possible, it is preferable to provide an antireflection layer on the a-Si photoconductive layer. As the material for forming the antireflection layer, a-Si
In addition to the conditions that it does not adversely affect the photoconductive layer and has excellent antireflection properties, it must also have electrophotographic properties, such as resistance above a certain level, and when liquid development is used, It has excellent solvent resistance, and furthermore, it has already been formed within the conditions for forming an antireflection layer.
- Conditions such as not degrading the characteristics of the Si-based photoconductive layer are required.

Furthermore, in order to make antireflection effective, it is clear from simple optical calculation that the material for forming the antireflection layer should have a refractive index between that of the a-Si layer and that of air. It is good to choose as it exists.

Further, the layer thickness is preferably set to /4n or an integer multiple thereof, but considering the light absorption of the antireflection layer itself, it is optimal to set it to /4n. (However, n is the refractive index of the a-Sj layer, and in is the wavelength of the exposure light.

) Considering such optical conditions, the thickness of the antireflection layer is preferably 50 to 10 h, assuming that the wavelength of the exposure light is approximately within the wavelength range of visible light. be.

In the present invention, materials that can be effectively used as antireflection layer forming materials include, for example, M is 2, A is 203, and Z
^Co2, Ti〇2, ZnS, Ce〇2, CeF2, Si
Inorganic fluorides and inorganic oxides such as 02, Si○, Ta24, AsoF3, and SuaF, or polyvinyl chloride, polyamide resin, polyimide resin, vinylidene chloride, melamine resin, epoxy resin, phenolic resin, celery acetate Examples include organic compounds such as

The electrophotographic photoreceptor 1 shown in FIG. 1 has a structure in which the a-Si photoconductive layer 3 has a free surface 4.
A surface coating layer such as a protective layer or an electrically insulating layer may be provided on the surface of the Si-based photoconductive layer 3, as in some conventional electrophotographic photoreceptors. An electrophotographic photoreceptor having such a surface coating layer is shown in FIG. The electrophotographic photoreceptor 5 shown in FIG. Although it is not essentially different from the electrophotographic photoreceptor 1 shown in FIG. 1, the characteristics required of the surface coating layer 8 differ depending on the electrophotographic process to which it is applied.

That is, for example, Japanese Patent Publication No. 42-23910, No. 43
If an electrophotographic process such as that described in Japanese Patent No. 124748 is applied, the surface coating layer 8 must be electrically insulating and have sufficient electrostatic charge retention ability when subjected to charging treatment. However, if an electrophotographic process such as the Carlson process is applied, it is desirable that the potential of the bright area after electrostatic image formation is very small, so the surface coating layer is required to have a certain thickness or more. 8 is required to be very thin. In addition to satisfying its desired electrical properties, the surface coating layer 8
Consideration should be given to not having any adverse chemical or physical effects on the i-based photoconductive layer, electrical contact and adhesion with the a-Si based photoconductive layer, as well as moisture resistance, abrasion resistance, and cleanability. It is formed by Typical materials that are effectively used as surface coating layer forming materials include polyethylene terephthalate, polycarbonate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, polyamide, polytetraethylene, and polyethylene terephthalate. Ethylene trifluoride chloride, polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-ethylene tetrafluoride copolymer
, trifluoroethylene-vinyl IJDene copolymer, synthetic resins such as polybutene, polyvinyl butyral, and polyurethane, and cellulose conductors such as diacetate and triacetate. These synthetic resins or cellulose derivatives may be formed into a film and laminated onto the a-Si photoconductive layer, or a coating liquid may be formed and a
- It may be applied to the Si-based photoconductive layer 7 to form a stiffness. The layer thickness of the surface coating layer is appropriately determined depending on the desired characteristics and the material used, but is usually 0.
It is said that there are about 5 to 70 mountains. In particular, when the surface coating layer is required to function as the above-mentioned protective layer, in the normal case,
It is set to be 10 or less, and on the other hand, when a function as an electrical insulating layer is required, it is usually set to 10 or more. However, the layer thickness value that distinguishes between the protective layer and the electrically insulating layer varies depending on the materials used, the applied electrophotographic process, and the structure of the electrophotographic photoreceptor, and is different from the above-mentioned value of 10 mm. is not absolute. Moreover, this surface coating layer 8
If it also plays the role of an anti-reflection layer as mentioned above, its function will be further expanded and it will become more effective.

Next, the case where the electrophotographic photoreceptor of the present invention is manufactured by a glow discharge method and a sputtering method will be explained.

FIG. 3 is a schematic explanatory diagram of a glow discharge deposition layer for manufacturing the electrophotographic photoreceptor of the present invention by a capacitance type glow discharge method. Reference numeral 10 denotes a glow discharge deposition tank, in which a substrate 11 for forming an a-Si photoconductive layer is fixed to a fixing part 12;
A heater 13 for heating the substrate 11 is installed on the lower side of the board.

Capacitance type electrodes 15, 15' connected to a high frequency power source 14 are wound around the upper part of the vapor deposition tank 10, and when the high frequency power source 14 is turned on, the electrodes 15, 15' are connected to a high frequency power source 14.
A high frequency wave is applied to 15' to generate a glow discharge in the vapor deposition tank 10. A gas introduction pipe is connected to the upper end of the hollyhock tank 10, and gas cylinders 16,1
From 7 and 18, when the gas in each cylinder is needed, it is transferred to the vapor deposition tank 1.
It is designed to be introduced within 0.

Reference numerals 19, 20, and 21 are flow meters for detecting the flow rate of gas, and 22, 23, and 24 are flow meters.
is a valve, 25, 26, 27 are valves, and 28 is an auxiliary valve.

Further, the lower end of the vapor deposition tank 10 is connected to an exhaust device (not shown) via a main valve 29.

301 is a valve for covering the vacuum inside the vapor deposition tank 10.

In order to form an a-Si photoconductive layer with desired characteristics on a substrate 11 using the glow discharge apparatus shown in FIG. and fix it to the fixing member 12.

In order to clean the surface of the substrate 11, a commonly practiced method, for example, a chemical treatment method using American acid or acid, etc., is employed. Alternatively, after being cleaned to some extent, it may be placed in a predetermined position in the vapor deposition tank 10, and glow discharge treatment may be performed before forming an a-Si photoconductive layer thereon. In this case, the process from cleaning the substrate 11 to forming the a-Si photoconductive layer can be carried out in the same system without breaking the vacuum, thereby avoiding dirt and impurities from adhering to the cleaned substrate surface. I can do it. After fixing the substrate 11 to the fixing member 12, the main valve 29 is fully opened to exhaust the air in the deposition tank 10 to bring the vacuum level to about -10-kiorr. Vapor deposition tank 10
After the interior reaches a predetermined degree of vacuum, the heater 13 is ignited to heat the substrate 11, and once it reaches a predetermined temperature, it is maintained at that temperature. Next, fully open the auxiliary valve 28, and then open the gas cylinder 16.
fully open the valve 25 of the gas cylinder 17 and the valve 26 of the gas cylinder 17.

The gas cylinder 16 is for Ar gas, and the gas cylinder 17 is for raw material gas for forming a-Si, for example,
SiH4, Si 2 days 6, Si 4 days. Or a mixture thereof is stored. Further, the cylinder 18 is for raw material gas for producing impurities to be introduced into the a-Si photoconductive layer as required, and stores PH3, P2 ratio, B2 day 6, etc. After that, the flow rate control valves 22 and 23 of the gas cylinders 16 and 17 are gradually opened while watching the flow meters 19 and 20, and Ar gas and a-Si system such as Si gas are formed in the vapor deposition tank 10. Introduce raw material gas for

At this time, Ar gas is not necessarily required, and only the source gas may be introduced. When introducing Ar gas mixed with raw material gas for a-Si formation such as SiH4 gas,
The quantitative ratio is determined as desired, but usually the raw material gas is 10Vo% or more relative to the Ar gas. Note that He gas may be used instead of Ar gas. At the time when gas is introduced into the vapor deposition tank 10 from the cylinders 16 and 17, the main valve 29 is adjusted,
A predetermined degree of vacuum is maintained at 10-2 to $orr in the normal case, which is the raw material gas pressure for forming a-Sj.

Next, a predetermined frequency is applied to the electrodes 15, 15 of the capacitor stub wound outside the vapor deposition tank 10 by the high frequency power source 14.
In normal cases, when a glow discharge is caused in the vapor deposition tank 10 by applying a high frequency of 0.2 to 30 MHz, for example, Si specific gas is decomposed and Si is vapor deposited on the substrate 11 to form an a-Si layer. be done. When introducing impurities into the a-Si-based photoconductive layer to be formed, an impurity-generating gas may be introduced from the cylinder 18 into the vapor deposition tank 10 at the time of forming the a-Si-based photoconductive layer.

In this case, by appropriately adjusting the flow rate control valve 24, the amount of gas introduced into the deposition tank 10 from the cylinder 18 can be appropriately controlled.
In addition to being able to arbitrarily control the amount of impurities introduced into the a-Si photoconductive layer, it is also possible to easily change the amount of impurities in the thickness direction of the a-Si photoconductive layer. Third
In the glow discharge deposition layer shown in the figure, RF (r
adiofrequency) Capacitance type glow discharge method is adopted, but in addition to this, RF inductance type and DC two-pole type are used.

Glow discharge methods such as the above are also employed in the present invention. Further, the electrode for glow discharge may be provided outside the vapor deposition tank 10 or may be provided inside the vapor deposition tank 10. In the present invention,
Groups that are considered valid. In order to obtain one discharge, the current density must be set to 0.
It is best to use an AC or DC current of 1~1 hA/, and in order to obtain sufficient power, 300~5000V.
Since the characteristics of the a-Si photoconductive layer to be formed greatly depend on the substrate temperature during growth, it is preferable to strictly control the voltage.

In the present invention, the substrate temperature is usually 50 to 35,000,
Preferably in the range of 100 to 200 qo, the a-S has effective properties as a photoconductive layer for electrophotography.
An i-based photoconductive layer is formed. In addition, the growth rate of the a-Si layer is also a factor that greatly influences the physical properties of the a-Si layer.
In order to achieve the purpose of the present invention, in the normal case, 0.5 to 100
A/sec, preferably 1 to 50 A/sec. FIG. 4 is a schematic explanatory diagram showing one of the apparatuses for manufacturing the electrophotographic photoreceptor of the present invention by a sputtering method. Reference numeral 31 denotes a vapor deposition tank, in which a substrate 32 for forming an a-Si photoconductive layer is fixed to an electrically insulating fixing member 33 and placed at a predetermined position.

A heater 34 for heating the substrate 32 is arranged below the substrate 32, and above the substrate 32 is arranged at a predetermined interval.
A polycrystalline or single-crystalline silicon target 35 is placed at a position facing the . A high frequency power source 36 applies high frequency waves between the substrate 32 and the silicon target 35 . Further, the vapor deposition tank 31 includes a cylinder 37.
, 38 are valves 39, 40, flow meters 41,
42, flow control valves 43, 44, and an auxiliary valve 45, gas is introduced into the deposition tank 31 from cylinders 37, 38 when necessary. Now, in order to form an a-Si photoconductive layer on the substrate 32 using the apparatus shown in FIG. and evacuate to the specified degree of vacuum.

Next, the heater 34 is ignited to heat the substrate 32 to a predetermined temperature. When forming an a-Si photoconductive layer by sputtering, the heating temperature of the substrate 32 is usually 50 to 350 qo, preferably 100 to 200 qo. This substrate temperature affects the growth rate of the a-Si layer, the structure of the layer, the presence or absence of voids, etc., and is one of the factors that determines the quality of the a-Si layer formed, so it must be sufficiently controlled. . 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 stage of forming the a-Si layer, the substrate temperature is kept at a relatively low temperature T, and once the a-Si layer has grown to a certain extent, the substrate temperature is raised to a temperature higher than T, and the a-Si layer is form a layer, a
At the final stage of -Si layer formation, the substrate temperature is lowered again to a temperature lower than T2, thereby forming an a-Si photoconductive layer. By changing the thickness, it is possible to continuously change the electrical and optical properties of the a-Si photoconductive layer in the layer thickness direction. Furthermore, since the layer growth rate of a-Si is slower than that of other materials such as Se, when the formed layer becomes thicker, the a-Si formed at the initial stage of layer formation (a-Si closer to the substrate side) There is a strong possibility that Si) may change the characteristics at the initial stage of layer formation until the end of layer formation, so in order to form an a-Si layer with uniform characteristics in the thickness direction, It is desirable to form the layer while increasing the substrate temperature from the beginning to the end of the layer formation.

Next, after detecting that the substrate 32 has been heated to a predetermined temperature, the main valve 46, the auxiliary valve 45, the valve 39
,40 fully opened.

Next, & gas is introduced into the vapor deposition tank 31 from the gas cylinder 38 while adjusting the main valve 46 and the flow control valve 44 until the vacuum level is reduced to a predetermined level, and the vacuum level is maintained at that level.
Subsequently, the valve 43 is opened and gas is introduced into the vapor deposition tank 31 from the cylinder 37 until the vacuum level is reduced to a predetermined level, and the vacuum level is maintained.

In this case, the flow rates of the Ar gas and the Ar gas into the vapor deposition tank 31 are appropriately determined so that an a-Si photoconductive layer having desired physical properties is formed. For example, the pressure of Ar and the mixed gas in the vapor deposition tank 31 is a degree of vacuum, which is usually 10-3 to 10
-ltorr, preferably rr of 5 x 10-3 to 3 x 10-2. Ar gas can also be replaced with He gas or the like. After Ar gas and 2 gas are introduced into the vapor deposition tank 31 from the cylinders 37 and 38 until a predetermined degree of vacuum is reached, the high frequency power supply 36 supplies the vapor with a predetermined frequency and voltage.
A high frequency is applied between the substrate 32 and the silicon target 35 to cause a discharge, and the generated Ar ions sputter the Si of the silicon target to form an a-Si film on the substrate 32.

In the construction 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 in the present invention is usually 0.2 to 30 MHZ, preferably 5 to 20 MHZ, and the discharge current density is usually 0.2 to 30 MHZ.
It is desirable that it be 1 to 1 hA/, preferably 1 to 5 mA/. Also, in order to obtain sufficient power, 300-5
It is preferable to adjust the voltage to 000V. The growth rate of the a-Si layer when manufacturing the electrophotographic photoreceptor of the present invention by the sputtering method is mainly determined by the substrate temperature and discharge conditions, and it influences the physical properties of the formed layer. This is one of the major factors. The growth rate of the a-Si film to achieve the purpose of the present invention is usually 0.5~
It is desirable that the current is 100 A/sec, preferably 1 to 50 A/sec. In the sputtering method, as in the glow discharge method, the a-Sj photoconductive layer formed can be adjusted to be n-type or p-type by doping with impurities.

The method of introducing impurities is the same in the sputtering method as in the glow discharge method, for example, PH3, P2 day 4,
When the a-Si layer is formed, a gas such as BH6 is introduced into the vapor deposition tank 31 to dope P or B as an impurity into the a-Si layer. In addition, a-Si formed
Impurities may be introduced into the layer by an ion plantation method. In this case, since the extremely thin surface layer of the a-Sj layer can be easily controlled to have a specific conductivity type, for example,
It is advantageous because the charge retention layer of an electrophotographic photoreceptor as described in Japanese Patent Publication No. 49-6223 can be formed very easily, and its characteristics can be arbitrarily controlled. Hereinafter, the present invention will be specifically explained with reference to Examples.

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

The surface was treated with a 1% NaOH solution, thoroughly washed with water and dried to clean the surface. Thickness: 1 skin, size: 1
An aluminum substrate measuring 0 cm x 10 cm was prepared and firmly fixed at a predetermined position of a fixing member 12 at a predetermined position in a glow discharge deposition tank 10 at a distance of about 10 cm from a heater 13 .

Next, the main valve 29 was fully opened to exhaust the air in the deposition tank 10, resulting in a degree of vacuum of approximately 5×10 −5 rr.

Thereafter, the heater 13 was ignited to uniformly heat the aluminum substrate to 150°C, and the temperature was maintained at that temperature.
After that, the auxiliary valve 28 is fully opened, and the cylinder 16 is then opened.
After fully opening the valve 22 of the cylinder 17 and the valve 26 of the cylinder 17,
Gradually open the flow rate control valves 22 and 23 to
Ar gas was introduced into the vapor deposition tank 10 through the cylinder 6, and SiH 4 gas was introduced into the vapor deposition tank 10 through the cylinder 17. At this time, the main valve 29 was adjusted so that the degree of vacuum in the vapor deposition tank 10 was maintained at about 0.75 ton. Subsequently, the switch of the high frequency power supply 14 was turned off, and a high frequency of 13.58 MHZ was applied between the electrodes 15 and 15' to generate a glow discharge, thereby forming an a-Si layer on the aluminum substrate.

The glow discharge current at this time is about 8 hA/, so the voltage is 200
It was 0V. Also, the growth rate of the a-Si layer at this time is
Vapor deposition was performed at about 4 A/sec for 1 hour to form an a-Si layer with a thickness of 20 mm on the aluminum substrate. After the completion of vapor deposition, the electrophotographic photoreceptor produced in this manner is exposed to the outside by closing the main valve 29, valves 25, 26, and valves 22, 23, and opening the valve 30 instead to break the vacuum in the vapor deposition tank 10. I took it out. To this electrophotographic photoreceptor, we applied an e-corona discharge with a power supply voltage of 5500V to a-Si.
The photoconductive layer is imaged on the surface of the photoconductive layer, and then imagewise exposed at an exposure dose of 15 seconds to form an electrostatic image. When the image was transferred and fixed to a computer, an extremely clear image with high resolution was obtained. When this image forming process was repeated on the electrophotographic photoreceptor and the durability of the electrophotographic photoreceptor was tested, the image obtained on the 10,000th sheet of transfer paper was also of extremely good quality. There was no difference when compared to the image on the first sheet of transfer paper, proving that this electrophotographic photoreceptor is extremely durable with excellent corona ion resistance, abrasion resistance, and cleanability.

For cleaning, blade cleaning was used, and the blade was molded from urethane rubber. Next, the electrophotographic photoreceptor described above was subjected to corona discharge in oil at a power supply voltage of 6000V, and then
When image exposure was carried out with a light intensity of EC and the image was produced under the same conditions as when the image was produced using e-corona discharge as described above, the image on the transfer paper obtained was lower than that obtained with e-corona charging. was.

From this experiment, it was found that the electrophotographic photoreceptor obtained in this example had charge polarity dependence. Example 2 After forming an a-Si layer with a thickness of 20 mm on an aluminum substrate under the same conditions and procedures as in Example 1, the evaporation tank 10 was
The sample was taken out, and a polycarbonate resin was applied onto the a-Si layer so as to have a thickness of 15 peaks after drying, thereby forming an electrically insulating layer to obtain an electrophotographic photoreceptor.

As a primary charge on the surface of the insulating layer of this photoreceptor, a power supply voltage of 6
■Corona discharge at 000V. When I went during this EC,
Therefore, it was charged to 2000V. Next, as secondary charging, e-corona discharge is performed at a power supply voltage of 5500 V, and at the same time, the exposure amount is 15
Image exposure was carried out at aux.sec, and then the entire surface of the photoreceptor was uniformly irradiated to form an electrostatic image. When this electrostatic image was developed with toner charged to e by a cascade method and transferred and fixed onto transfer paper, an image of extremely high quality was obtained. Example 3 Similar to Example 1, the apparatus shown in FIG. 3 was used. An electrophotographic photoreceptor of the present invention was prepared in the following manner, and an image was formed by performing an image forming process. 1% N
The surface was treated with a solution called aOH, thoroughly washed with water, and dried to clean the surface.It has a thickness of 1 rib and a size of 10 arcs x 10.
An aluminum substrate having a diameter of 1.5 cm was prepared and firmly fixed at a predetermined position of a fixing member 12 in a predetermined position in a glow discharge deposition tank 10 at a distance of about 10 cm from a heater 13.

Next, the main valve 29 was fully opened to exhaust the air in the deposition tank 10, resulting in a degree of vacuum of about 5 x 10-5 Wrr.

Thereafter, the heater 13 was ignited to uniformly heat the aluminum substrate to a temperature of 150 oo and maintained at this temperature. After that, fully open the auxiliary valve 28, and then open the cylinder 1.
After fully opening the valve 25 of No. 6 and the valve 26 of the cylinder 17, the flow control valves 22 and 23 were gradually opened to introduce A gas from the cylinder 16 and SiH4 gas from the cylinder 17 into the deposition tank 10. At this time, the main valve 29 was adjusted so that the degree of vacuum in the vapor deposition tank 10 was maintained at approximately 0.75 rr.Also, in this case, while watching the flow meters 19 and 20, By adjusting 22 and 23, the Si ratio gas flow rate is 10Vo% of the M gas flow rate.
I made it so that Next, the valve 27 of the cylinder 18 is fully opened, and then the flow rate control valve 24 is gradually opened to control the flow rate to be 5×10-3Vo% of the flow rate of SiH4 gas, while the vapor deposition tank 6 gases were introduced into the building.

At this time as well, the main valve 29 was adjusted to maintain the degree of vacuum in the vapor deposition tank 10 at 0.75 tons. Subsequently, the switch of the high frequency power supply 14 was turned on and a high frequency of 13.58 MHZ was applied between the electrodes 15 and 15' to generate a glow discharge and form an a-Si layer on the aluminum substrate. The glow discharge current at this time was about 3 mA/, and the voltage was 1500V. Also, the growth rate of the a-Si layer in this case is approximately 4
A/sec and time evaporation was performed for one period to form a 20 mm thick a-Si layer on the aluminum substrate. After the completion of vapor deposition, the electrophotographic photoreceptor produced in this way is connected to the main valve 29, the flow rate adjustment valves 22, 23, 24, and the valve 25.
, 26 and 27 were closed, and the valve 30 was opened instead to break the vacuum inside the vapor deposition tank 10 and take it out to the outside. This electrophotographic photoreceptor was subjected to e-corona discharge on the surface of the a-Si photoconductive layer at a power supply voltage of e5500V in the floor, and then imagewise exposed at an exposure amount of 20 cux·sec to form an electrostatic image. was formed, and the electrostatic image was developed with differentially charged toner by a cascade method and transferred and fixed onto transfer paper, resulting in an extremely clear image. Repeating this image forming process,
When the durability of the electrophotographic photoreceptor was tested, the image obtained on the 10,000th sheet of transfer paper was also of extremely good quality, and compared to the image on the first sheet of transfer paper. There was no difference when compared, demonstrating that this electrophotographic photoreceptor is extremely durable.

As the cleaning method, blade cleaning was used, and the blade was molded from urethane rubber. Next, the above electrophotographic photoreceptor was subjected to corona discharge at a power supply voltage of 6000 V during 8 sounds, and then 20 times
Image exposure was performed at an exposure amount of sec to form an electrostatic image.

This electrostatic image was developed using e-charged toner by a cascade method, and then transferred and fixed onto transfer paper, resulting in an extremely clear image. From this result and the previous results, it was found that the electrophotographic photoreceptor obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar photoreceptor.

Example 4 In the same manner as in Example 3, except that the flow rate of the B2 specific gas was adjusted to 5xlo-4vok% of the flow rate of the Si specific gas, a 20% thick film was formed on an aluminum substrate. An electrophotographic photoreceptor was prepared by forming an a-Si photoconductive layer.

Regarding this electrophotographic photoreceptor, an image was formed on a transfer paper under the same conditions and procedures as in Example 3. The image quality was excellent and extremely clear. From this result, it was found that the electrophotographic photoreceptor obtained in this example had charge polarity dependence.

However, the polarity dependence was opposite to that of the electrophotographic photoreceptor obtained in Example 1. Example 5 After forming an a-Si layer with a thickness of 20 mm on an aluminum substrate under the same conditions and procedures as in Example 4, the evaporation tank 1 was
After drying, a polycarbonate resin was applied onto the a-Si layer to form an electrically insulating layer, and an electrophotographic photoreceptor was obtained.

As a primary charge on the surface of the insulating layer of this photoreceptor, a power supply voltage of 6
000V and e-corona discharge to 0. I went to $ec,
Therefore, it was charged to 2000V. Next, as secondary charging, corona discharge is performed at a power supply voltage of 5500 V, and at the same time, the exposure amount is 15
Image exposure was carried out at a similar rate of sec, and then the entire surface of the photoreceptor was uniformly irradiated to form an electrostatic image. When this electrostatic image was developed with toner charged using a cascade method and transferred and fixed onto transfer paper, an extremely high quality image was obtained. Example 6 In Example 1, the substrate temperature was set to the following first value.
Sample No. 1 was prepared under the same conditions and procedures as in Example 1, except for various changes as shown in the table. Electrophotographic photoreceptors shown in (1) to (2) were prepared, and images were formed on transfer paper under exactly the same image forming conditions as in Example 3, and the results shown in Table 1 below were obtained.

As can be seen from the results shown in Table 1, in order to achieve the object of the present invention, the substrate temperature must be in the range of 50 to 3500°
- It is necessary to form an Sj layer.

Table 1 ◎=Aya ○: Good △: Can be used practically.

×: Not possible In Example 3, the electrophotographs shown by sample Nos. A photoreceptor was prepared, and an image was formed on a transfer paper under exactly the same image forming conditions as in Example 3, and the results shown in Table 2 below were obtained. As can be seen from the results shown in Table 2, in order to achieve the object of the present invention even in the case of this example, it is necessary to form the a-Si layer at a substrate temperature in the range of 50 to 350 qo. There is.

Table 2 ◎: Excellent ○: Good △: Can be used practically.

×: Impossible example 8 Example 4 except that the substrate temperature was variously changed as shown in Table 3 below.
Sample No. Electrophotographic photoreceptors shown in (1) to (2) were prepared, and images were formed on transfer paper under exactly the same image forming conditions as in Example 4, and the results shown in Table 3 below were obtained.

As can be seen from the results shown in Table 3, even in the case of this example, in order to achieve the object of the present invention, it is necessary to form the a-Si layer at a substrate temperature in the range of 50 to 350 oo. There is.

Table 3 ◎: Old woman ○: Good △: Can be used practically.

×: Impossible Example 9 An aluminum cylinder measuring 1,500 mm x 30 mm on the 2-thickness side is rotatably installed in the glow discharge deposition layer shown in FIG. A heater was installed to heat the cylinder.

Next, the main valve 29 was fully opened to exhaust the air in the deposition tank 10, resulting in a degree of vacuum of about 5xlo-50rr.

Thereafter, the heater 13 was ignited and at the same time the cylinder was rotated at a speed of 3 revolutions per minute to uniformly heat the cylinder to 15,000 ℃ and maintained at this temperature. After that, the auxiliary valve 28 is fully opened, and then the valve 25 of the cylinder 16 and the valve 26 of the cylinder 17 are fully opened, and then the flow rate adjustment valves 22 and 23 are gradually opened to supply Ar gas from the cylinder 16 and from the cylinder 17. Deposition tank 10 for SjH4 gas
introduced within. At this time, the main valve 29 was adjusted so that the degree of vacuum in the vapor deposition tank 10 was maintained at about 0.75 torr. Further, the Si gas flow rate was adjusted to be 1% of the gas flow rate. Next, after fully opening the valve 27 of the cylinder 18, while watching the flow meter 21, gradually open the flow rate adjustment valve 24 so that the flow rate becomes 10% of the flow rate of SiH4 gas for vapor deposition. Gas was introduced into the tank 10.

At this time as well, the main valve 29 was adjusted so that the degree of vacuum in the vapor deposition tank 10 was maintained at about 0.75 cc.

Subsequently, the switch of the high frequency power source 14 was turned on to apply a high frequency of 13.58 MHZ between the electrodes 15 and 15' to generate a glow discharge and form an a-Si layer on the cylinder substrate.

At this time, the glow discharge current is about 3 mA/c, and the voltage is 15
It was 00V. In addition, the growth rate of the a-Si layer in this case was set to about 2.5 A/sec, and the deposition was performed for 23 hours.
An a-Si layer with a thickness of 20 mm was formed on a cylinder substrate.
After the completion of vapor deposition, the electrophotographic photoreceptor created in this way is
Main valve 29, flow rate adjustment valves 22, 23, 24
, the valves 25, 26, and 27 were closed, and the valve 30 was opened instead to break the vacuum inside the deposition tank 10 and take it out to the outside.
This electrophotographic photoreceptor has a power supply voltage of e55 in 8 tones.
E-corona discharge is applied to the surface of the a-Si photoconductive layer at 00 V, and then image exposure is performed at an exposure dose of 20 x sec to form an electrostatic image, and the electrostatic image is charged by a cascade method. When the resulting toner was developed and transferred and fixed onto transfer paper, an extremely clear image was obtained. When this image forming process was repeated on the electrophotographic photoreceptor and the durability of the electrophotographic photoreceptor was tested, the image obtained on the 10,000th sheet of transfer paper was also of extremely good quality. There was no difference in comparison with the image on the first sheet of transfer paper, proving that this electrophotographic photoreceptor is extremely durable.

As the cleaning method, blade cleaning was used, and the blade was molded from urethane rubber. Next, the electrophotographic photoreceptor described above was subjected to corona discharge at a power supply voltage of 6000 V in 8 sounds, and then 20
When image exposure was carried out with a light intensity of sec and the image was produced under the same conditions as when the image was produced by applying the e-corona discharge described above, the resulting image on the transfer paper was lower than that in the case of e-corona charging. was.

From this experiment, it was found that the electrophotographic photoreceptor obtained in this example had a dependence on charging property. Example 10 In Example 3, the amount of B doped into the formed a-Si layer is shown in Table 4 below by varying the flow rate of the SiH4 gas with respect to the flow rate of the SiH4 gas. The same conditions and sample No. 3 as in Example 3 were used, except that the values were controlled to various values as shown. Electrophotographic photoreceptors shown in ■ to ■ were prepared.

When these were used to form an image on transfer paper under the same image forming conditions as in Example 3, the results shown in Table 4 were obtained.

As can be clearly seen from these results, for electrophotographic photoreceptors that can be used practically, the a-Si layer contains 10-6 B.
Preferably, the doping is in an amount in the range of 10-3 atomic%. Table 4 ◎: Excellent ○: Good ×: Unsatisfactory Example 11 Using the apparatus shown in Fig. 4, an electrophotographic photoreceptor of the present invention was prepared as follows, and an image was formed by performing an image forming process. Ta.

The surface was treated with a 1% NaOH solution, thoroughly washed with water, and dried to clean the surface.It has a thickness of 1 rib and a size of 1.
Approximately 1000△ in advance on the aluminum slope of 0c x 10 skin
A substrate on which Mo was deposited thickly was prepared and firmly fixed at a predetermined position of a fixing member 33 in a predetermined position in a vapor deposition tank 31 at a distance of about 10 skins from a heater 34 .

Further, the distance was about 8.5 skin from the polycrystalline silicon target 35 with a purity of 5 nines.

Next, the air in the vapor deposition tank 31 is exhausted to about 1×10-6
The vacuum level was set to rr. Thereafter, the heater 34 was ignited to uniformly heat the substrate to 150 qC, and the temperature was maintained at this temperature. After that, the auxiliary valve 45 is fully opened, and then the valve 40 of the cylinder 38 is fully opened, and then the flow rate adjustment valve 44 is gradually opened and the main valve 46 is used to gradually open the flow rate adjustment valve 44 to supply gas from the cylinder 38 into the vapor deposition tank 31. The degree of vacuum is 5.
It was introduced into the vapor deposition tank 31 at an rr of 5xlo-4. Subsequently, after fully opening the valve 39, the flow rate adjustment valve 43 is gradually opened while watching the flow meter 41 so that the degree of vacuum in the vapor deposition tank 31 becomes 5×10-3 tons, and the mountain gas is poured into the vapor deposition tank 31. introduced within.

After that, the switch of the high frequency power supply 36 is turned on, and 13.
A high frequency of 58 MHZ and IKV was applied to generate a discharge, and formation of an a-Si layer on the aluminum substrate was started. At this time, the growth rate of the a-Sj layer was controlled to about 2 μm/sec,
This was done continuously for 3 field hours. The resulting a-Si
The thickness of the layer was 20 Buddhas. The electrophotographic photoreceptor of the present invention prepared in this manner was subjected to a power supply voltage of 550V in the dark.
E-corona discharge was carried out, and then image exposure was carried out at a light intensity of 15 ux·sec to form an electrostatic image.

When this electrostatic image was developed using toner charged by the cascade method and then transferred and fixed onto transfer paper, an extremely clear and high quality image was obtained. Example 20 In Example 11, the amount of doping into the formed a-Si layer is shown in Table 5 below by varying the flow rate of the 2 gas with respect to the flow rate of the Ar gas. Electrophotographic photoreceptors shown in Samples ① to ① were prepared under the same conditions as in Example 11, except that various values were controlled as shown.

When these were used to form an image on transfer paper under the same image forming conditions as in Example 11, the results shown in Table 5 were obtained.

As is clearly seen from these results, the a-Si layer contains 10 to 4 days of sunlight as a practical exposure photoreceptor.
It is desirable that the doping be done in an amount in the range of 5% of the melon mic. Table 5 ◎: Excellent 0: Good △: May be cloudy in practical use.

X: Unacceptable Example 21 The electrophotographic photoreceptors prepared in Examples 1, 3, and 4 were heated at a temperature of 4000 and a humidity of 90 RH%.
It was left in a hot and humid atmosphere.

After 9 hours had elapsed, images were formed on transfer paper using the same conditions and procedures as in each example for each photoreceptor. A good image was obtained.

These results demonstrate that the electrophotographic photoreceptor of the present invention is also extremely excellent in terms of moisture resistance. Example 2
2 An electrophotographic photoreceptor prepared in exactly the same manner as in Example 1 was subjected to e-corona discharge in oil at a power supply voltage of 6,000 V, and then subjected to image exposure at an exposure dose of 20 ux·sec and left still. An electrostatic image was formed, and the electrostatic image was developed using a liquid developer in which a chargeable toner was dispersed in an isoparaffinic hydrocarbon solvent, and the electrostatic image was transferred and fixed onto a transfer paper.

The image thus obtained on the transfer paper had extremely high resolution, clarity, and high quality. Furthermore, in order to test the solvent resistance (liquid development resistance) of the electrophotographic photoreceptor, the above image forming process was repeated, and the image on the previous transfer paper and the image on the 10,000th sheet of transfer paper were compared. However, no difference was observed, demonstrating that the electrophotographic photoreceptor of the present invention has excellent solvent resistance.

As a cleaning method for the photoreceptor, a blade cleaning method was applied, and a blade made of urethane rubber was used.

[Brief explanation of the drawing]

1 and 2 are schematic structural sectional views showing an example of a preferred embodiment of the electrophotographic photoreceptor of the present invention, and FIGS. 3 and 4 are diagrams for manufacturing the electrophotographic photoreceptor of the present invention. FIG. 2 is a schematic explanatory diagram showing an example of the device. 1,5...Electrophotographic photoreceptor, 2,6...Support, 3,7...
- Photoconductive layer, 8... surface coating layer, 4, 9... free surface,
10, 31... Vapor deposition tank, 14, 36... High frequency power supply. Wealth diagram Figure 2 Riding diagram Figure 4

Claims (1)

[Scope of Claims] 1. Comprising a support and a photoconductive layer made of amorphous silicon containing 10 to 40 atomic percent hydrogen and having dark resistance and photosensitivity to which atomic photography can be applied. An electrophotographic photoreceptor featuring: 2. The electrophotographic photoreceptor according to claim 1, further comprising a surface coating layer. 3. The electrophotographic photoreceptor according to claim 1, further comprising an antireflection layer. 4. The electrophotographic photoreceptor according to claim 1, further comprising a layer having a refractive index between that of the photoconductive layer and that of air. 5. The electrophotographic photoreceptor according to claim 1, further comprising a barrier layer. 6. The electrophotographic photoreceptor according to claim 1, wherein the photoconductive layer contains impurities. 7 Claim 6, wherein the impurity is an n-type impurity
The electrophotographic photoreceptor described in . 8. The electrophotographic photoreceptor according to claim 6, wherein the impurity is an element belonging to Group III A of the periodic table. 9 The elements belonging to Group III A of the periodic table are B, Al
, Ga, In, and Tl. 10. The electrophotographic photoreceptor according to claim 6, wherein the impurity is an element belonging to Group V A of the periodic table. 11 The elements belonging to Group V A of the periodic table are N, P,
The electrophotographic photoreceptor according to claim 10, which is selected from among As, Sb, and Bi. 12. The electrophotographic photoreceptor according to claim 6, wherein the content of the element belonging to Group III A of the periodic table is 10^-^6 to 10^-^3 atomic %. 13 The content of the element belonging to Group V A of the periodic table is 1
The electrophotographic photoreceptor according to claim 6, wherein the content is 0^-^8 to 10^-^5 atomic %. 14. The electrophotographic photoreceptor according to claim 1, wherein the photoconductive layer has a layer thickness of 5 to 80 μm. 15. The electrophotographic photoreceptor according to claim 3, wherein the antireflection layer has a layer thickness of λ/4√(n) or several times thereof (where n is the refractive index of the photoconductive layer and λ is wavelength of incident light)
. 16. The electrophotographic photoreceptor according to claim 3, wherein the antireflection layer has a layer thickness of 50 to 60 mμ. 17. The electrophotographic photoreceptor according to claim 2, wherein the surface coating layer has a thickness of 0.5 to 70 μm. 18 A tank with a vacuum level of 10^-^ where a support for layer formation is arranged and a gas of a silicon compound containing hydrogen is introduced.
Under 2-3 torr, current density 0.1-10 mA/c
m^2, a voltage of 300 to 5000 V is generated to decompose the silicon compound.
on said support maintained within a temperature range of 50°C;
A method for manufacturing an electrophotographic photoreceptor, comprising forming a photoconductive layer made of amorphous silicon containing 10 to 40 atomic percent hydrogen. 19 The silicon compound is SiH_4, Si_2H_6
, Si_4H_1_0. The method for manufacturing an electrophotographic photoreceptor according to claim 18. 20. The method for manufacturing an electrophotographic photoreceptor according to claim 18, wherein a gas for introducing impurities is further introduced during the formation of the photoconductive layer. 21 The gas for introducing impurities is PH_3, P_2H
_4, B_2H_6. The method for manufacturing an electrophotographic photoreceptor according to claim 20. 22. The method for manufacturing an electrophotographic photoreceptor according to claim 18, wherein an inert gas is introduced in addition to the silicon compound gas. 23. The method for manufacturing an electrophotographic photoreceptor according to claim 22, wherein the inert gas is either Ar gas or He gas. 24. The method for manufacturing an electrophotographic photoreceptor according to claim 18, wherein hydrogen gas is further introduced during the formation of the photoconductive layer. 25. The method for producing an electrophotographic photoreceptor according to claim 18, wherein the surface of the support is exposed to electric discharge before the formation of the photoconductive layer. 26 Claim 18, wherein the discharge is an alternating current discharge
The method for producing an electrophotographic photoreceptor as described in 2. 27 Claim 18, wherein the discharge is a direct current discharge
The method for producing an electrophotographic photoreceptor as described in 2. 28 In a tank where a support for forming a layer and a target containing silicon are arranged, and a gas for introducing hydrogen is introduced,
Under vacuum level 10^-^3~10^-^1 torr, current density 0.1~10mA/cm^2, voltage 300~50
By generating a discharge under a discharge condition of 00V and sputtering the target with ions generated by the discharge, 10% A method for producing an electrophotographic photoreceptor, comprising forming a photoconductive layer made of amorphous silicon containing up to 40 atomic percent hydrogen. 29. The method for manufacturing an electrophotographic photoreceptor according to claim 28, wherein the inert gas is either Ar or He. 30. The method for manufacturing an electrophotographic photoreceptor according to claim 28, wherein the hydrogen introduction gas is hydrogen gas. 31. The method for manufacturing an electrophotographic photoreceptor according to claim 28, wherein the gas for introducing hydrogen is silicon hydride. 32 The silicon compound is SiH_4, Si_2H_6,
The method for manufacturing an electrophotographic photoreceptor according to claim 31, wherein the electrophotographic photoreceptor is selected from Si_4H_1_0. 33. The method for manufacturing an electrophotographic photoreceptor according to claim 28, wherein the discharge is an alternating current discharge.