JPS6215855B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing an amorphous photoconductive member that is sensitive to electromagnetic waves such as light (here, light in a broad sense refers to ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.). Photoconductive materials constituting photoconductive layers in image pickup tubes for televisions, image forming members for electrophotography, etc.
It must have high sensitivity, high resistance, and spectral characteristics as close as possible to the visual sensitivity, and it must be non-polluting to the human body during manufacturing and use. Characteristics such as being able to easily control within time are required. In particular, in the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine,
Pollution-free property during the above-mentioned use is an important point. However, it is a conventional photoconductive material that constitutes the photoconductive layer of a commercially available image pickup tube.
PbO, Se-As-Te, CdSe, Sb ₂ S ₃ , etc., and inorganic photoconductive materials such as Se, CdS, and ZnO, which are photoconductive materials that constitute the photoconductive layer of electrophotographic image forming members, and poly-N vinyl. It is difficult to assert that organic photoconductive materials (OPC) such as carbazole (PVK) and trinitrofluorenone (TNF) necessarily satisfy all of the above conditions to a higher level. For example, in the case of an electrophotographic image forming member, in an electrophotographic image forming member using Se as a photoconductive layer forming material, if Se alone is used, for example, when light in the visible light region is used, Since the spectral sensitivity range is narrow, attempts are being made to widen the spectral sensitivity range by adding Te or As. 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 result in a decrease in the image density of the copied image or background stains (fogging on white areas), and if you continue to copy other documents, the image of the previous document may be copied as an afterimage ( It has disadvantages such as ghost phenomenon). 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 immediately rubbed and rubbed during processing such as cleaning, and a portion of it will be scraped off, preventing development. They may get mixed into agents, be scattered inside copying machines, or be mixed into copied images, resulting in 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. Alternatively, if the surface of the photoconductive layer is exposed, when a liquid developer is used to visualize (develop) an electrostatic image, it will come into contact with the solvent, resulting in poor solvent resistance (liquid development resistance). Although excellent properties are required, it is difficult to say with certainty that Se-based photoconductive layers are necessarily satisfactory in this respect. Separately, since Se-based photoconductive layers are usually formed by vacuum deposition, in order to obtain a photoconductive layer with desired photoconductive properties with good reproducibility, the deposition temperature and the deposition substrate temperature must be adjusted. It is necessary to strictly adjust various manufacturing parameters such as , degree of vacuum, and cooling rate. In addition, the Se-based photoconductive layer is formed in an amorphous state in order to have high dark resistance as a photoconductive layer of an electrophotographic image forming member, but Se crystallization occurs at an extremely low temperature of approximately 65°C. Therefore, crystallization occurs during handling after manufacturing or during use, and is greatly affected by the ambient temperature and frictional heat caused by rubbing with other parts during the image forming process. However, it also has a drawback in terms of heat resistance, in that it tends to cause 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 image-forming member having a so-called binder-based photoconductive layer is advantageous in manufacturing compared to an image-forming member having an Se-based photoconductive layer, and can be manufactured at a relatively low manufacturing cost. That is, the binder-based photoconductive layer is prepared by applying a coating solution prepared by kneading ZnO or CdS particles and a suitable resin binder using a suitable solvent onto a suitable substrate, using a doctor blade method, Datesvink method, etc. Since it can be formed by simply applying and solidifying it using the coating method described above, compared to image forming members with Se-based photoconductive layers, it is not necessary to invest as much capital in manufacturing equipment, and the manufacturing method itself is simple. And it's 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 nature of the formation, there are many parameters that determine the electrical and photoconductive properties as well as the physical and chemical properties of the photoconductive layer, and therefore, these parameters must be precisely adjusted to achieve the desired results. There is a drawback that a photoconductive layer having specific characteristics cannot be formed with good reproducibility, leading to a decrease in yield and a lack of mass productivity. Furthermore, due to the unique nature of the binder-based photoconductive layer being a dispersed system, the entire layer is porous, and as a result, it is highly dependent on humidity, resulting in deterioration of electrical properties when used in a humid atmosphere. In many cases, it becomes impossible to obtain a copy of the 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 penetrates into the layer together with its carrier solvent due to capillary action, so the above-mentioned problem becomes significant, and it becomes 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 bolus 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 to prevent it from coming into contact with the human body or scattering into the surrounding environment during manufacturing and use. It is necessary to
When using ZnO, there is almost no effect on the human body, but ZnO binder-based photoconductive layers have low photosensitivity, a narrow spectral sensitivity range, and significant light damage.
It has drawbacks such as poor photoresponsiveness. In addition, in electrophotographic image forming members using organic photoconductive materials such as PVK and TNF, which have recently been attracting attention, PVK, TNF, etc. This method has the advantage in manufacturing that a photoconductive layer can be formed simply by forming a coating film of an organic photoconductive material, and the advantage that an electrophotographic image forming member with excellent flexibility can be manufactured. On the other hand, it lacks moisture resistance, corona ion resistance, and cleaning properties, and has drawbacks such as low photosensitivity, the spectral sensitivity region in the visible light region is sandwiched, and it is biased toward the short wavelength side. However, it is only used in a very limited range. However, some of these organic photoconductive materials are suspected of being carcinogenic, and there is no guarantee that many of them are completely harmless to the human body. Therefore, there is a need for a third material that can provide an excellent photoconductive member that overcomes the above-mentioned problems. Among the materials that have recently been viewed as promising are amorphous silicon (hereinafter a-Si).
). In the early stages of development, a-Si films showed a variety of electrical and optical properties due to their structure being influenced by the manufacturing method and manufacturing conditions, which caused major problems 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. As a result, it did not receive much attention as a research material for basic physical properties, and no research and development was conducted for its application. However, it was thought that p and n control was impossible in amorphous a-
In early 1976, it was reported that a p-n junction could be realized for the first time in amorphous silicon (Applied Physics Letter; Vol. 28, No. 2,
15January, 1976), there has been a great deal of interest in this technology, and research and development efforts have since focused primarily on its application to solar cells. For this reason, the a-Si films reported so far are
Since it was developed for use in solar cells, it cannot currently be used as a photoconductive layer in electrophotographic image forming members or image pickup tubes due to its electrical and optical properties. It is. In other words, solar cells convert solar energy into current and extract it, so in order to have a good signal-to-noise ratio [photocurrent (ip)/dark current (id)] and extract current efficiently, an a-Si film is required. The resistance must be relatively small, but if the resistance is too small, the photosensitivity will decrease and the signal-to-noise ratio will deteriorate, so one of its characteristics is that the resistance is 10 ⁵
~ ^108Ω . cm is required. However, an a-Si film with this level of resistance (dark resistance: resistance in a dark place) has too much resistance (dark resistance) to be used as a photoconductive layer in, for example, an electrophotographic image forming member or an image pickup tube. ) is so low that currently known electrophotographic methods cannot be used at all. Furthermore, in previous reports on a-Si films, increasing the dark resistance lowers the photosensitivity; for example, when the dark resistance increases to 10 ¹⁰ Ω. cm, the photoelectric gain (photocurrent per incident photon) of the a-Si film is reduced, and in this respect, the conventional a-Si film is not suitable for use in electrophotographic image forming members, image pickup tubes, etc. It could not become a conductive layer. Therefore, a method for producing an a-Si layer having sufficient dark resistance and photosensitivity to be used as a photoconductive layer in electrophotographic image forming members, image pickup tubes, etc. is required, taking into account reproducibility and productivity. It is necessary to develop Incidentally, the a-Si layer is generally formed on a suitable support by a deposition method utilizing a discharge phenomenon such as a glow discharge method or a sputtering method. When forming an a-Si layer by such a deposition method, various reports and literature have shown that the dark resistance and photosensitivity of the formed layer change depending on the temperature of the support during layer formation. ing. That is, for example, if the support temperature is maintained at a high temperature of about 300°C to form a layer, it is one of the electrical characteristics.
It is possible to measure the increase in the SN ratio. However, a-Si
The layer growth rate of , for example, is much slower than that of Se, etc., so the high temperature described above can be kept constant and precise until the layer thickness required for the photoconductive layer of electrophotographic image forming members, image pickup tubes, etc. is achieved. It is extremely difficult to maintain. Furthermore, in the case of a photoconductive layer of an electrophotographic imaging member, the total light-receiving surface area may normally be e.g.
Since it requires a large area, larger than A4 or B4 size, it is currently not possible to control the temperature in order to uniformly maintain the high temperature state shown above until the layer formation is completed over such a large area. This technique is extremely difficult to achieve.
However, even when changing the support temperature,
It is difficult to even control the rate of temperature change over such a large area so that there is no variation in temperature depending on location. As described above, it is extremely difficult to control the support temperature at high temperature for a long time and over a large area without temperature unevenness in order to obtain the desired dark resistance, bright resistance, and photosensitivity. Therefore, temperature unevenness occurs depending on the location and time during layer formation, and it is not only impossible to make the layer thickness uniform over a large area, but also make it difficult to make the electrical and optical properties required for the photoconductive layer uniform. I can't even do that. The present invention has been made in view of the above-mentioned points, and the present invention can be realized by heat-treating an a-Si layer formed by a predetermined method at a specific temperature (Ta) in a specific atmosphere. The invention is primarily based on the discovery that a photoconductive layer having the desired excellent properties can be obtained. Furthermore, the present invention is suitable for use as a photoconductive layer for electrophotographic image forming members, image pickup tubes, etc., which is formed at a support temperature near room temperature (T _R ), where temperature control is relatively easy, since the electrical properties are extremely poor. a-Si, which cannot be conventionally applied to
It has also been discovered that even if the layer is formed, if heat treatment is performed at a certain temperature (Ta) and atmosphere after the layer is formed, the required electrical characteristics can be fully satisfied. Furthermore, it has been found that a photoconductive layer that is electrically and optically uniform over the entire desired area can be formed without strict temperature control during heat treatment. The present invention provides a method for producing a photoconductive member that has always stable electrical and optical properties, extremely high sensitivity, excellent optical fatigue resistance and heat resistance, and does not cause deterioration even after repeated use. The main purpose is to provide Another object of the present invention is to provide a photoconductive member which, when applied to an electrophotographic image forming member, can easily produce high-quality images with high density, clear halftones, and high resolution. An object of the present invention is to provide a manufacturing method that can obtain the obtained results. Another object of the present invention is to provide a method for producing a photoconductive member having a spectral sensitivity region covering substantially the entire visible light region, a low dark decay rate, and a fast photoresponsiveness. Yet another object of the present invention is to provide a method for producing a photoconductive member having excellent abrasion resistance, cleaning properties, and solvent resistance. Amorphous photoconductive member of the present invention (hereinafter referred to as a-
A method for producing a photoconductive member (hereinafter referred to as a photoconductive member) includes an a-Si layer formed on a support with at least one of oxygen, nitrogen, and a compound containing an oxygen atom or a nitrogen atom.
The a-photoconductive member is produced by heat treatment in an atmosphere containing at least one of the activated materials. Alternatively, the method for producing an a-photoconductive member of the present invention includes: (a) introducing a desired gas into a deposition chamber that can be reduced in pressure to achieve a desired internal pressure; (b) Forming a gas plasma atmosphere in the space where either one exists; (b) A-Si
(c) maintaining the gas plasma atmosphere for a sufficient time to deposit the a-Si layer on the support formed in step (b); heat treating the layer in an atmosphere containing at least one of oxygen, nitrogen and a compound containing oxygen atoms or nitrogen atoms, or an activated one thereof; The a-photoconductive member is formed by a manufacturing method including the following. In the present invention, a-
An amorphous photoconductive layer (hereinafter referred to as an a-photoconductive layer) is formed by subjecting the Si layer to a heat treatment that will be described in detail below. Support temperature during formation
Ts and the temperature Ta at which the heat treatment is performed after layer formation are basically determined by taking reproducibility and productivity into consideration as well as the mutual relationship that allows a photoconductive layer having desired characteristics to be obtained. The upper limit of Ts is usually 100°C, preferably 50°C. As for the lower limit of Ts, if it is too low, not only will the surface properties of the a-Si layer deteriorate, but the physical properties of the layer formed at such a temperature will be lower than that of the photoconductive layer of electrophotographic image forming members, image pickup tubes, etc. If the temperature is too far from T _R , it will require cooling control, so in normal cases It is better to refer to T _R. still,
In the present invention, T _R refers to 20 to 25°C. After forming the a-Si layer, the temperature Ta at which the heat treatment is performed is within a range that achieves the desired electrical and optical properties that can achieve the purpose of the present invention, as well as electrophotographic properties when applied to electrophotography. The temperature may be selected as appropriate, but it is usually 100°C or higher, preferably 150°C or higher. As for the upper limit of Ta, the formed a-Si layer is
The temperature is not so high as to adversely affect the desired properties, typically 450°C, preferably 400°C.
It is desirable that this is done. In particular, 200 ~ as Ta
A temperature in the range of 350°C is optimal. In the present invention, the heat treatment time is as follows:
Although it varies depending on the thickness and area of the layer formed, the type of support on which the layer is formed, etc., it is generally good to set the time to 15 to 180 minutes. In the present invention, the formed a-Si layer is formed with an annealing atmosphere forming substance or/and an activated version thereof as described below in order to undergo a post-layer heat treatment. exposed to a harsh atmosphere. To heat-treat the a-Si layer in the above atmosphere, the support on which the a-Si layer is formed may be heated to Ta, or the a-Si layer may be placed for heat treatment. The temperature of the atmosphere (ambient temperature)
The temperature may be set to Ta, or both the temperature of the support and the temperature of the atmosphere may be set to Ta. In the present invention, the annealing atmosphere-forming substance that forms the atmosphere when heat-treating the a-Si layer formed on the desired support with the desired layer thickness and area is oxygen, nitrogen, oxygen atoms, or Examples include a compound containing a nitrogen atom, air, or a mixture thereof. In the present invention, this annealing atmosphere-forming substance may be used as it is as it normally exists as a gas, or may be converted into plasma, radicals, etc.
After activation and completion of the a-Si layer formation, it may be introduced into the same deposition chamber for forming the a-Si layer without breaking the vacuum and subjected to subsequent heat treatment (continuous method No. 1), or , the material inside the deposition chamber is introduced into a heat treatment chamber designed to be able to be transferred without breaking the vacuum, and heat treatment is continued (continuous method No. 2).
Alternatively, after forming the a-Si layer, it may be taken out of the deposition chamber for forming the a-Si layer into the atmosphere, and then introduced again into a heat treatment chamber provided separately from the deposition chamber for heat treatment. It is also good to go (discontinuous method). However, in order to further improve mass productivity and uniform characteristics of the a-Si layer formed, continuous method No. 2 is the most preferable among the above three heat treatment methods. The annealing atmosphere forming substance containing oxygen atoms or nitrogen atoms includes a formed during heat treatment.
- Almost any material can be used as long as it does not incorporate impurities unnecessary for achieving the purpose of the present invention into the Si layer or deteriorate the chemically or physically formed a-Si layer. obtain. As such an atmosphere-forming substance, it is preferable to use a substance that can take a gaseous state at room temperature. Specifically, examples of annealing atmosphere forming substances containing oxygen atoms or nitrogen atoms include ozone (O ₃ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), nitric oxide (NO),
Nitrous oxide ( _N2O ), nitrogen sesquioxide _{( N2O3} ), nitrogen trioxide _{( N2O4} ) _, nitrogen dioxide ( _NO2 ), nitrogen pentoxide ( _N2O5 ), ammonia ( _NH3) ), etc., and many others are valid. These may be used as a mixture of two or more types, if necessary, as long as they do not cause any inconvenience in achieving the object of the present invention. Under the above conditions, the heat-treated a-Si layer (a-photoconductive layer) has electrical properties that are suitable for use as a photoconductive layer in electrophotographic image forming members, image pickup tubes, etc. over a large area. and the optical properties are uniform, and such uniformity does not change over time, and, more importantly, when applied to an electrophotographic imaging member,
Because it has excellent electrostatic properties, corona ion resistance, solvent resistance, abrasion resistance, cleaning properties, etc., there is almost no deterioration in electrophotographic properties due to repeated use. As described above, the photoconductive layer formed by the manufacturing method of the present invention is useful as a photoconductive layer for electrophotographic image forming members, image pickup tubes, etc., but it is also useful as a photoconductive layer for solid-state image sensors. It is also useful for composing sections. In the present invention, the a-photoconductive layer is formed on the support described below. For example, stainless steel, Al, Cr, Mo, Au, Ir,
A conductive support such as metals such as Nb, Ta, V, Ti, Pt, Pd or alloys thereof, or these metals,
Effective examples include vapor-deposited conductive supports, heat-resistant films or sheets of synthetic resins exhibiting heat resistance at least in Ta, and electrically insulating supports such as glass and ceramics.
The support is subjected to a series of cleaning treatments before the a-Si is deposited thereon. In such a cleaning treatment, generally, for example, if the support is made of metal,
Contact with an alkaline or acidic solution effectively cleans the surface by etching. after that,
The support is dried in a clean atmosphere and, without any further preparatory treatment, is then a-
It is installed at a predetermined position within the deposition chamber of an apparatus for depositing Si onto a support. In the case of an electrically insulating support, its surface is subjected to conductive treatment, if necessary. For example, in the case of glass, its surface is conductively treated with In ₂ O ₃ , SnO _2, etc., or in the case of synthetic resin film such as polyimide film, it is treated with Al, Ag,
Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V,
The surface is treated with a metal such as Ti or Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, so that the surface thereof is conductive. The shape of the support body is cylindrical, belt-shaped,
It may have any shape, such as a plate shape, and the shape is determined as desired. However, in the case of electrophotography, it is preferable to use an endless belt shape or a cylindrical shape for continuous high-speed copying. The thickness of the support is appropriately determined so that the desired a-photoconductive member is formed, but if flexibility is required as the a-photoconductive member, the thickness of the support may be It is made as thin as possible as long as it is within the range of sufficient performance. 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. In the present invention, in order to deposit a-Si on a support installed in a deposition chamber to form an a-Si layer with a desired thickness, first, a predetermined pressure is set in the deposition chamber, for example, 1×10 ^- After reducing the pressure to about ³ to 1 × 10 ^-8 Torr, the support is maintained at a temperature Ts, and then a predetermined gas is introduced into the deposition chamber to cause a discharge phenomenon, thereby discharging at least one of silicon and silicon compounds. A gas plasma atmosphere may be formed in the existing space within the deposition chamber, and the gas plasma atmosphere may be maintained for a sufficient period of time until a desired layer thickness is achieved. Deposition methods that utilize discharge phenomena include glow discharge method, sputtering method, ion plating method, etc.
A Si layer is formed on the support by such a deposition method. In the present invention, in order to generate a discharge phenomenon in the deposition chamber that is effective for forming a desired plasma atmosphere, an AC or DC power source is used, and in order to obtain sufficient power, it is usually 100 to 2000 V, preferably. is 300~1500V
The voltage adjusted to the voltage and the input power are usually 0.1 to 300 W, preferably 0.5 to 100 W. Furthermore, in the case of AC, the frequency is usually 0.2 to 30 MHz, preferably 5 to 20 MPH.
It is desirable that this is done. In the present invention, the a-Si layer to be heat-treated is formed of one type of a-Si semiconductor of the following types, or at least two types are selected, and different types are bonded. It can be obtained by forming layers as a state. N-type: containing only a donor;
Or one that contains both a donor and an acceptor and has a high donor concentration (Nd). P-type: Contains only acceptor. Or one that contains both Doto and acceptor and has a high concentration of acceptor (Na). Type i...NaNdO or NaNd. The a-Si semiconductor layer of the type ~ as a layer constituting the photoconductive layer in the present invention is formed by n-type impurities during layer formation by a glow discharge method, a reactive sputtering method, etc., as will be described in detail later. Alternatively, it can be formed by doping a p-type impurity or both impurities into the a-Si semiconductor layer to be formed by controlling the amount thereof. In this case, according to the findings from the experimental results of the present inventors, by adjusting the impurity concentration in the layer within the range of 10 ¹⁵ to 10 ¹⁹ cm ³ , stronger n-type (or stronger A weaker n-type (or weaker p-type) a-Si layer can be formed from a p-type a-Si layer. The type of a-Si layer is prepared by glow discharge method,
It is formed by a sputtering method, an ion implantation method, an ion plating 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 desired electrical and optical characteristics of the a-photoconductive member to be manufactured. However, it is relatively easy to control to produce an a-Si photoconductive member having desired characteristics. The glow discharge method is preferably employed because of its advantages such as being able to introduce impurities of the group 1 or 2 in a substitutional manner. Furthermore, in the present invention, the glow discharge method and the sputtering method are used together in the same equipment system to achieve a-
A Si layer may also be formed. The formed a-Si layer has desired properties, and its dark resistance and photoelectric gain are controlled by incorporating H during its formation. Here,
"H is contained in the a-Si layer" means that
Either "a state in which H is combined with Si", "a state in which H is ionized and incorporated into the layer", or "a state in which H is incorporated into the layer as _H2 ", or a combination thereof. It means the state of being. The inclusion of H in the a-Si layer is achieved by introducing H into the manufacturing equipment system in the form of compounds such as SiH ₄ and Si ₂ H ₆ or H ₂ when forming the layer.
The gas discharge decomposes these compounds or H ₂ and incorporates them into the a-Si layer as the layer grows. According to the findings of the present inventors, the H content in the a-Si layer is one of the major factors that determines whether the formed a-photoconductive member can be applied in practice. and has proven to be extremely important. In the present invention, in order to make the formed a-photoconductive member sufficiently applicable to practical applications, the amount of H contained in the a-photoconductive layer is usually 10 to 10%.
It is desirable that the content be 40 atomic %, preferably 15 to 30 atomic %. The theoretical basis for the reason why the H content in the a-photoconductive layer is limited to the above-mentioned numerical range has not yet been clarified and remains in the realm of speculation. However, from numerous experimental results, it has been found that with an H content outside the above numerical range, it is extremely difficult to control the properties to meet the requirements of a photoconductive layer of an image forming member for electrophotography, for example. The produced electrophotographic image forming member has extremely low sensitivity to irradiated electromagnetic waves, or in some cases, the sensitivity is hardly recognized, or the increase in carrier due to electromagnetic wave irradiation is small, etc. It has been proven that it is a necessary condition that the H content is within the above numerical range. For example, in the glow discharge method, hydrogen compounds such as SiH ₄ and Si ₂ H ₆ are used as starting materials for forming a-Si, so H _is contained in the a-Si _layer. Hydrogen compounds such as H ₆ decompose and a-
When the Si layer is formed, H is automatically contained in the layer, but in order to more efficiently contain H into the layer, glow discharge is performed when forming the a-Si layer. All you have to do is introduce _H2 gas into the equipment system. When using the sputtering method, H ₂ gas is introduced when sputtering is performed using Si as a target in an atmosphere of an inert gas such as Ar or a mixed gas based on this gas, or
A silicon hydride gas such as SiH ₄ or 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. The a-Si layer can be controlled to the above types by doping with impurities during manufacturing. In order to make the a-Si layer P-type, suitable impurities to be doped into the a-Si layer include elements from group A of the periodic table, such as B, Al, Ga, In, and Tl. In the case of n-type, elements of group V A of the periodic table, such as N, P, As,
Preferred examples include Sb and Bi. The amount of impurity doped into the a-Si layer is
It is determined as appropriate 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 to 10 ^-3 atomic%, preferably 10 ^-5 to 10 -3 atomic%.
10 ^-4 atomic%, in the case of impurities of group A of the periodic table, usually 10 ^-8 to 10 ^-3 atomic%, preferably 10 ^-8 to
It is desirable to set it to 10 ^-4 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, and specifically,
This will be explained in detail in the following description or examples. a-The thickness of the photoconductive layer depends on the desired electrical and optical properties, electrophotographic properties when applied to electrophotography, and use conditions, such as whether flexibility is required. Although it is determined appropriately depending on the
μ, preferably 10 to 50 μ. Next, the case where the glow discharge method and the sputtering method are adopted in the present invention will be explained. FIG. 1 is a schematic illustration of an apparatus for manufacturing an a-photoconductive member by a capacitance type glow discharge method. 101 is a glow discharge deposition chamber, inside of which a support 102 for forming an a-photoconductive layer is fixed to a fixing member 103;
A heater 104 for heating the support body 102 is installed on the lower side of the support body 102 so as to be electrically insulated from the fixing member 103 . A fixing member 103 on which the support 102 is installed is provided so as to be movable up and down as shown by an arrow It is now possible to place . Deposition chamber 10
Capacitance type electrodes 106 and 107 connected to a high-frequency power source 105 are wound on the upper part of the electrode 1, and when the high-frequency power source 105 is turned on, high-frequency power is applied to the electrodes 106 and 107 to cause deposition. A glow discharge is generated within the chamber 101. A heat treatment chamber 127, which is a chamber for heat treating the a-Si layer formed in the deposition chamber 101, is connected to the left side of the deposition chamber 101. Deposition chamber 10
1 and the heat treatment chamber 127 without breaking the vacuum.
It is designed so that by opening and closing the gate valve 136, the contents inside can be moved or it can be made into an independent chamber. 128 is a heating furnace used when heat-treating the a-Si layer in the heat treatment chamber 127, and for example, infrared heating means or heating means with a built-in heater can be used. A gas introduction pipe is connected to the left end extension of the heat treatment chamber 127 so that an annealing atmosphere forming substance is introduced into the heat treatment chamber 127 from a cylinder 129 . 130 and 135 are valves, 132 is a flow control valve, and 131 is a flow meter. An inductance coil 134 connected to a high frequency power source 133 is wound between the flow rate control valve 131 and the valve 135 of the gas introduction pipe, and introduces an annealing atmosphere forming substance from the cylinder 129 into the heat treatment chamber 127. At this time, the atmosphere-forming substance can be activated in advance by turning it into plasma or radicals, if necessary. 138 is an auxiliary heating furnace, and the heat treatment chamber 12
This is a means for preheating the annealing atmosphere forming substance or its activated substance introduced into the heat treatment chamber 127 to a predetermined temperature before introducing it into the heat treatment chamber 127. In order to form an a-photoconductive layer with desired characteristics on the support 102 using the apparatus shown in FIG. It is fixed to the fixing member 103. To clean the surface of support 102, typically
Practical methods, such as chemical treatment methods using neutral detergent solutions, pure water, alkalis, acids, etc., are employed. After cleaning to some extent, the deposition chamber 101
A glow discharge treatment may be performed before the a-photoconductive layer is formed on the a-photoconductive layer. In this case, since the process from cleaning the support 102 to forming the a-photoconductive layer can be carried out in the same system without breaking the vacuum, it is possible to avoid dirt and impurities from adhering to the cleaned support surface. I can do it. After the support body 102 is fixed to the fixing member 103, the main valve 125 is fully opened to exhaust the air in the deposition chamber 101 as shown by arrow A, and the degree of vacuum is approximately 10 ^-5 Torr. After the inside of the deposition chamber 101 reaches a predetermined degree of vacuum, the heater 104 is ignited as necessary to heat the support 102, and when the temperature reaches a predetermined temperature, it is maintained at that temperature. Next, fully open the auxiliary valve 124, and then open the valve 120 of the gas cylinder 108 and the gas cylinder 109.
fully open the valve 121. The gas cylinder 108 is for dilution gas such as Ar gas, and the gas cylinder 109 is for raw material gas for forming a-Si, such as SiH ₄ , Si ₂ H ₆ , Si ₄ H ₁₀ or the like. mixtures etc. are stored. Also, cylinder 11
0 and cylinder 111 are for raw material gas for introducing impurities into the a-photoconductive layer as necessary,
PH ₃ , P ₂ H ₄ , B ₂ H ₆ etc. are stored. After that, the flow rate adjustment valve 1 of the gas cylinders 108 and 109
16, 117, flow meters 112 and 113
While observing the situation, the deposition chamber 101 is gradually opened and a diluent gas such as Ar gas and SiH ₄ gas, for example, is introduced into the deposition chamber 101.
A raw material gas such as gas for forming a-Si is introduced. At this time, a diluent gas such as Ar 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 general, the raw material gas with respect to dilution gas is introduced. Gas is considered to be 10Vol% or more. Note that a rare gas such as He gas may be used instead of Ar as the diluent gas. At the time when gas is introduced into the deposition chamber 101 from the cylinders 108 and 109, the main valve 1 is opened.
25 to the specified degree of vacuum, in the normal case,
Maintain the gas pressure at 10 ^-2 to 3 Torr when forming the a-Si layer. Next, capacitance type electrodes 106 and 107 wound outside the deposition chamber 101 are supplied with a predetermined frequency, usually 0 or 2, by a high frequency power source 105.
When a glow discharge is caused in the deposition chamber 101 by applying a high frequency voltage of ~30 MHz, for example, SiH ₄ gas is decomposed and Si is deposited on the support 102 to form a-Si.
A layer is formed. When introducing impurities into the a-Si layer to be formed, an impurity-generating gas may be introduced into the deposition chamber 101 from the cylinder 110 or 111 at the time of forming the a-Si layer. In this case, by appropriately adjusting the flow rate control valve 118 or 119, the amount of gas introduced into the deposition chamber 101 from the cylinder 110 or 111 can be appropriately controlled. In addition to being able to arbitrarily control the amount of impurities introduced therein, it is also possible to easily change the amount of impurities in the thickness direction of the a-Si layer. A gas introduction pipe is connected to the upper end of the deposition chamber 101, so that the gas in each cylinder is introduced into the deposition chamber 101 from the gas cylinders 108, 109, 110, and 111 when necessary. 112,113,114,1
15 are flowmeters for detecting the flow rate of gas, and 116, 117, 1
18 and 119 are flow rate adjustment valves, and valve 124 is an auxiliary valve. Also, the lower end of the deposition chamber 101 has a main valve 125.
via an exhaust system (not shown). 126 is a valve for breaking the vacuum in the deposition chamber 101. Next, after an a-Si layer with a predetermined thickness is formed on the support 102, the high frequency power source 105 is turned off and the valves 116, 117, 118, and 124 are closed. In this case, the heater 104 for maintaining the temperature of the support 102 may be left in the ON state or may be turned OFF. Next, the main valve 141 is fully opened and the gate valve 13 is placed at the position shown by the dotted line in the heat treatment chamber 127, which has been evacuated to a predetermined degree of vacuum as shown by the arrow B.
6 is opened and the a-Si layer formed on the support 102 is transferred by a pair of rotating rollers 139 and a series of multiple rotating rollers 140. Gate valve 136 is then closed again. In this case, the heat treatment chamber 127 may be heated in advance by the heating furnace 128, or the a-Si
The temperature increase may be started after the layer is moved from the deposition chamber 101 to the position indicated by the dotted line and the gate valve 136 is closed. In the heat treatment chamber 127 into which the a-Si layer has been introduced, the valves 130 and 135 are fully opened, and the flow meter 13 is opened.
1, the flow rate control valve 132 is gradually opened, an annealing atmosphere forming substance is introduced from inside the cylinder 129, the flow rate control valve 132 and the main valve 141 are adjusted to a predetermined internal pressure, and the heat treatment is carried out. is started. Heat treatment chamber 1 in this case
Even if the internal pressure of 27 is higher than atmospheric pressure,
Further, the pressure may be reduced to below atmospheric pressure. Next, after the a-Si layer is heat-treated for a predetermined time, the flow control valve 132 and the valve 135 are closed, and the heating furnace 128 is turned off. After that, the support body 102 is moved in the direction of the take-out lid 137 by the rotating roller 140, cooled to a predetermined temperature, the main valve 141 is closed, the leak valve 142 is gradually opened, and the take-out lid 137 is opened. The a-photoconductive layer (heat-treated a-Si layer) formed on the support 102 is taken out to the outside. In the device shown in Figure 1, RF (radio
Although a capacitance type glow discharge method (frequency) is employed, other glow discharge methods such as an RF inductance type and a DC bipolar type are also employed in the present invention. Further, the electrode for glow discharge may be provided inside the deposition chamber 101 or may be provided outside the deposition chamber 101. FIG. 2 is a schematic explanatory diagram showing one of the apparatuses for manufacturing an a-photoconductive member by the sputtering method in the present invention. 201 is a deposition chamber, and a support 202 for forming an a-photoconductive layer is inside the deposition chamber 201.
A conductive fixing member 2 that is electrically insulated from
03 and installed at a predetermined position. A heater 204 for heating the support 202 is arranged below the support 202, and a polycrystalline or single crystal silicon target 205 is placed above the electrode 2 at a position facing the support 202 with a predetermined interval.
It is installed in 06. Fixing member 203 on which support body 202 is installed
A high frequency voltage is applied between the silicon target 205 and the silicon target 205 by a high frequency power supply 207. Further, in the deposition chamber 201, there is a cylinder 20.
8, 209, 210, 211 are valves 21, respectively.
2,213,214,215, flow meter 21
6,217,218,219, flow rate adjustment valve 2
20, 221, 222, 223, auxiliary valve 22
4, and the cylinders 208, 20
9, 210, and 211, gas is introduced into the deposition chamber 201 when necessary. Note that the auxiliary valve 224 is also used in the device shown in FIG.
In the middle of the gas introduction pipe route between the
A means for activating the annealing atmosphere forming substance, for example, turning it into plasma or radicals, similar to the apparatus shown in the figure, is provided to activate the annealing atmosphere forming substance before introducing it into the deposition chamber 201. It's okay. Now, in order to form an a-photoconductive layer on the support 202 using the apparatus shown in FIG.
The air in the chamber is evacuated to a predetermined degree of vacuum as shown by arrow C using an appropriate exhaust device. next,
If necessary, the heater 204 is ignited to heat the support 2.
02 to a predetermined temperature. Next, after detecting that the support body 202 is maintained at a predetermined temperature, the auxiliary valve 224 and the valves 212 and 213 are fully opened. Next, while adjusting the main valve 225 and the flow control valve 221, H ₂ gas is introduced from the cylinder 209 into the deposition chamber 201 until a predetermined vacuum level is reached, and the vacuum level is maintained. Next, the flow control valve 220 is opened, and an atmospheric gas such as Ar gas is introduced from the cylinder 208 into the deposition chamber 201 until a predetermined degree of vacuum is reached.
Maintain that level of vacuum. In this case, H ₂ gas and
The flow rate of atmospheric gas such as Ar gas into the deposition chamber 201 is appropriately determined so that an a-Si layer having desired physical properties is formed. For example, the pressure of the mixed gas of atmospheric gas and H ₂ gas in the deposition chamber 201 is a degree of vacuum, usually 10 ^-3 to 10 ^-1 Torr, preferably 5 × 10 ^-3 to 3 ×
It is assumed to be 10 ^-2 Torr. Ar gas can also be replaced with rare gas such as He gas. After atmospheric gas such as Ar gas and H ₂ gas are introduced into the deposition chamber 201 from cylinders 208 and 209 until a predetermined degree of vacuum is reached, the high frequency power source 20
7, at a predetermined frequency and voltage, the support 20
A high frequency voltage is applied between the fixing member 203 and the silicon target 205 on which the silicon target 205 is installed, and the Si of the silicon target 205 is sputtered with the generated ions of the atmospheric gas such as Ar ions. An a-Si layer is formed on top. In the explanation of FIG. 2, a sputtering method using high frequency electric field discharge is used, but a sputtering method using DC electric field discharge may also be adopted.
In the sputtering method, as in the glow discharge method, a is formed by doping with impurities.
-Si 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,
Substances such as PH ₃ , P ₂ H ₄ , B ₂ H ₆ etc. in gaseous state a
- When forming the Si layer, it is introduced into the deposition chamber 201 from the cylinder 210 to dope P or B as an impurity into the a-photoconductive layer. In addition to this, impurities may also be introduced into the formed a-Si layer by ion implantation. In this case, the extremely thin surface layer of the a-Si layer can be easily controlled to have a specific conductivity type. Next, after an a-Si layer with a predetermined thickness is formed on the support 202, the high frequency power supply 207 is turned off, the valves 220, 221, and if necessary the valve 222 are closed, and the Exhaust the gas thoroughly. At this time, the heater 204 that maintains the temperature of the support 202 may continue to be in the ON state, or may be turned OFF. Thereafter, while maintaining the support body 202 at the heat treatment temperature Ta, fully opening the valve 215, and gradually opening the flow rate control valve 223, an annealing atmosphere forming substance is introduced into the deposition chamber 201 from the cylinder 211, and the main The valve 225 is adjusted to bring the internal pressure of the deposition chamber 201 to a predetermined pressure, and heat treatment is performed for a predetermined time. After performing heat treatment for a predetermined time, the flow rate adjustment valve 223 and the auxiliary valve 224 are closed, and the heater 2 is closed.
04 is turned off, and the a-Si layer (a-
photoconductive layer). Then, take it outside. Example 1 Using the apparatus shown in FIG. 1, an electrophotographic image forming member was prepared in the following manner, and an image was formed by performing an image forming process. An aluminum support with a thickness of 1 mm and a size of 34 cm x 27 cm, which had been surface-treated with a 1% NaOH solution, washed thoroughly with water, and dried to clean the surface, was prepared and placed in the glow discharge deposition chamber 101. It was firmly fixed at a predetermined position of a fixing member 103 located at a predetermined position inside. Next, the main valve 125 was fully opened to exhaust the air in the deposition chamber 101, resulting in a vacuum level of approximately 5×10 ⁻⁵ Torr. Thereafter, the heater 104 is ignited to uniformly heat the aluminum support to 50°C, and after maintaining this temperature, the auxiliary valve 124 is fully opened, and subsequently the valve 120 of the cylinder 108 and the valve 121 of the cylinder 109 After fully opening, gradually open the flow control valves 116 and 117 to supply Ar gas from cylinder 108 and SiH ₄ from cylinder 109.
Gas was introduced into the deposition chamber 101. At this time, the main valve 125 was adjusted so that the degree of vacuum in the deposition chamber 101 was maintained at approximately 0.07 Torr. Next, the switch of the high frequency power supply 105 is turned on, and the electrodes 106, 107 are connected to 13, . High frequency power of 56 MHz was applied to generate glow discharge inside the deposition chamber 101, resulting in an input power of 100 W. An a-Si layer is grown on the support 102 under these conditions,
The same conditions were maintained for 15 hours to form an a-Si (containing H) layer with a thickness of about 16 μm. Thereafter, while the inside of the deposition chamber 101 is evacuated, the high frequency power source 105 is turned on.
is turned OFF to stop glow discharge, and the flow rate adjustment valves 116, 117 and valve 12 are
0.121, the auxiliary valve 124 was closed, and the pressure inside the deposition chamber 101 was set to about 1×10 ^-5 Torr, and the vacuum level was maintained for 10 minutes. At this time, the temperature of the support was maintained at the temperature at the time of layer formation. During this time, the valve 141 was also opened in the heat treatment chamber 127 to exhaust air to create a vacuum of approximately 1×10 ⁻⁵ Torr. Thereafter, by opening the gate valve 136 and rotating the rotary rollers 139 and 140, the heating furnace 128 is heated to 250°C.
The support body 102 on which a-Si was deposited was moved to the position indicated by the dotted line in the heat treatment chamber 127 whose temperature was raised to °C,
Gate valve 136 was closed. valve 13 immediately
0.135 is fully opened, then gradually opens the flow control valve 132 and adjusts the main valve 141 while introducing O ₂ gas from the cylinder 129 to bring the internal pressure of the heat treatment chamber 127 to approximately 100 Torr, and heat treatment is performed in this state. maintained while doing so. 250 like this
Heat treatment was carried out at a temperature of 30 minutes. After the electrophotographic image forming member produced in this way is heat-treated, the support body 102 is moved toward the removal lid 137 by the rotating roller 140, and the valves 141, 130, flow rate adjustment valve 132, and valve 135 are closed. Instead, the leak valve 142 was opened to break the vacuum inside the heat treatment chamber 127 and take it out to the outside. On this electrophotographic image forming member, corona discharge was applied to the surface of the photoconductive layer in the dark with a power supply voltage of 5500 V.
Next, perform image exposure with an exposure amount of 15 lux・sec,
An electrostatic image is formed, and the electrostatic image is developed with charged toner using a cascade method and transferred onto transfer paper.
When it was fixed, an extremely sharp image with high resolution was obtained. When this image forming process was repeated on the electrophotographic image forming member and the durability of the electrophotographic image forming member was tested, the image obtained on the 100,000th sheet of transfer paper was also extremely poor. It is of good quality and there is no difference compared to the image on the first sheet of transfer paper.
This electrophotographic imaging member has corona ion resistance,
It has been demonstrated that it has excellent abrasion resistance, cleanability, etc., and is extremely durable. Note that blade cleaning was adopted as the cleaning method, and the blade was molded from urethane rubber. Example 2 Example 1 except that the conditions shown in Table 1 were used.
An a-Si layer was formed on the aluminum support under the same conditions and procedures as above, and then heat treated at the temperature shown in Table 2 for 60 minutes, and then taken out to prepare samples Nos. Electrophotographic image forming members shown in the following were obtained. Further, electrophotographic image forming members manufactured under the same conditions as Sample No. s~ except that no heat treatment was performed were used as comparative samples. For these electrophotographic image forming members, a power supply voltage of 550V is applied in the dark.
Corona discharge is applied to the photoconductive layer surface, and then
Image exposure is performed with an exposure amount of 15 lux sec to form an electrostatic image, and the electrostatic image is developed with charged toner by the cascade method and transferred and fixed onto transfer paper, and the resulting transferred image is I took up the position and conducted an evaluation. The results are shown in Table 2.

【table】

[Table] Evaluation: ◎...Excellent ○...Good △...Practically acceptable ×...Practically not possible Example 3 Aluminum After forming an a-Si layer on the support and subsequently performing heat treatment for 30 minutes at the temperature shown in Table 4, it was taken out and electrophotographic image forming members represented by sample Nos. Obtained. Further, electrophotographic image forming members manufactured under the same conditions as Sample No. s~ except that no heat treatment was performed were used as comparison samples. For these electrophotographic image forming members, corona discharge was applied to the photoconductive layer surface in the dark with a power supply voltage of 5500 V, and then
Image exposure is performed with an exposure amount of 15 lux sec to form an electrostatic image, and the electrostatic image is developed with charged toner using a cascade method to be transferred and fixed onto transfer paper, and the resulting transferred image is I took up the position and conducted an evaluation. The results are shown in Table 4.

【table】

[Table] Evaluation: ◎...Excellent ○...Good △...Practically acceptable ×...Practically unacceptable Example 4 Example 1 except for the conditions shown in Table 5
An a-Si layer was formed on the aluminum support under the same conditions and procedures as above, and then heat treated at the temperature and time shown in Tables 5 and 6, and then taken out and used as a sample. Electrophotographic imaging members designated by No. s~ were obtained. For these electrophotographic image forming members, corona discharge was applied to the surface of the photoconductive layer at a power supply voltage of 5500 V in the dark, and then 15 lux.
An electrostatic image is formed by performing image exposure with an exposure amount of sec, and the electrostatic image is developed with charged toner by a cascade method and transferred and fixed onto a transfer paper, and the resulting transferred image is , conducted an evaluation. The results are shown in Table 6.

【table】

[Table] Evaluation: ◎...Excellent ○...Good △...Practically acceptable ×...Practically not possible
Example 5 Example 1 except that the conditions shown in Table 7 were used.
An a-Si layer was formed on the aluminum support using the same conditions and procedures as above, followed by heat treatment at the temperatures and times shown in Tables 7 and 8, and then taken out to prepare the sample. Electrophotographic imaging members designated by No. s~ were obtained. For these electrophotographic image forming members, corona discharge was applied to the surface of the photoconductive layer at a power supply voltage of 5500 V in the dark, and then 15 lux.
An electrostatic image is formed by performing image exposure with an exposure amount of sec, and the electrostatic image is developed with charged toner by a cascade method and transferred and fixed onto a transfer paper, and the resulting transferred image is , conducted an evaluation. The results are shown in Table 8.

【table】

[Table] Evaluation: ◎...Excellent ○...Good △...Practically acceptable ×...Practically not possible
Example 6 Example 1 except that the conditions shown in Table 9 were used.
An a-Si layer was formed on the aluminum support under the same conditions and procedures as above, and then heat treated at the temperature and time shown in Tables 9 and 10, and then taken out and used as a sample. Electrophotographic imaging members designated by No. s~ were obtained. For these electrophotographic image forming members, corona discharge was applied to the surface of the photoconductive layer at a power supply voltage of 5500 V in the dark, and then 15 lux.
An electrostatic image is formed by performing image exposure with an exposure amount of sec, and the electrostatic image is developed with charged toner by a cascade method and transferred and fixed onto a transfer paper, and the resulting transferred image is , conducted an evaluation. The results are shown in Table 10.

【table】

[Table] Evaluation: ◎...Excellent ○...Good △...Practically acceptable ×...Practically not possible
Example 7 Using the auxiliary heating furnace 138, a- After the Si layer was formed and heat treatment was subsequently performed in the heat treatment chamber 127 at a temperature of 250° C. for 20 minutes, the vacuum in the heat treatment chamber 127 was broken and taken out to the outside. Corona discharge was applied to the photoconductive layer surface of this electrophotographic image forming member in the dark with a power supply voltage of 5500 V, and then image exposure was performed with an exposure amount of 15 lux·sec to form an electrostatic image. When the electric image was developed with toner charged by the cascade method, transferred and fixed onto transfer paper, an extremely clear image with high resolution was obtained. Example 8 Same as Example 1 except for heat treatment conditions in which the temperature of the core surrounded by the auxiliary heating furnace 138 is kept at 350°C during heat treatment and the heating furnace 128 is not turned on and the heat treatment chamber 127 is kept at room temperature. Forming an a-Si layer on the aluminum support according to the following conditional procedure, followed by heating at a gas temperature of 350°C in a heat treatment chamber 127.
After heat treatment was performed for 40 minutes, the vacuum inside the heat treatment chamber 127 was broken and the product was taken out to the outside. Corona discharge was applied to the photoconductive layer surface of this electrophotographic image forming member in the dark with a power supply voltage of 5500 V, and then 15 lux・sec
Image exposure is performed with an exposure amount of , to form an electrostatic image,
When the electrostatic image was developed with toner charged by the cascade method and transferred and fixed onto transfer paper, an extremely clear image with high resolution was obtained. Example 9 Similar to Example 1, using the apparatus shown in FIG.
An electrophotographic imaging member was prepared as follows,
Image formation processing was performed to produce an image. An aluminum support with a thickness of 1 mm and a size of 34 cm x 27 cm, which had been surface-treated with a 1% NaOH solution, washed thoroughly with water, and dried to clean the surface, was prepared and placed in the glow discharge deposition chamber 101. It was firmly fixed at a predetermined position of a fixing member 3 located at a predetermined position inside. Next, the main valve 25 is fully opened to open the deposition chamber 1.
The air in 01 was evacuated to create a vacuum of approximately 5×10 ^-5 Torr. Thereafter, the heater 104 was ignited to uniformly heat the aluminum support to 50° C., and the temperature was maintained at this temperature. After that, the auxiliary valve 12
4, and then open the valve 12 of the cylinder 108.
0. After fully opening the valve 121 of the cylinder 109,
Gradually open the flow control valves 116 and 117 to supply Ar gas from the cylinder 108 and the cylinder 109.
Then, SiH ₄ gas was introduced into the deposition chamber 101. At this time, the main valve 125 is adjusted so that the deposition chamber 10
The degree of vacuum inside 1 was maintained at approximately 0.07 Torr. Subsequently, the switch of the high frequency power supply 105 was turned on, and a high frequency power of 13.56 MHz was applied to the electrodes 106 and 107 to generate a glow discharge inside the deposition chamber 1, resulting in an input power of 100 W. An a-Si layer was grown on the support 102 under these conditions, and the same conditions were maintained for 15 hours to form an a-Si (containing H) layer with a thickness of about 16 μm. After that, the deposition chamber 1
While creating a vacuum inside 01, turn on the high frequency power supply 105.
The glow discharge is stopped as the OFF state, and the flow rate adjustment valves 116, 117 and the valve 12 are
0.121, the auxiliary valve 124 was closed, and the pressure inside the deposition chamber 101 was set to about 1×10 ^-5 Torr, and the vacuum level was maintained for 10 minutes. At this time, the temperature of the support was maintained at the temperature at the time of layer formation. After that, the gate valve 136 is opened, and the inside of the heat treatment chamber 127 is also removed from the deposition chamber 1.
The chamber was evacuated to the same degree of vacuum as inside 01.
Next, the valves 130 and 135 are fully opened, and then the flow rate adjustment valve 132 is gradually opened, and the main valve 25 is adjusted while the cylinder 129 is opened.
O ₂ gas is introduced to reduce the internal pressure of the deposition chamber 101 to approx.
The temperature was set at 100 Torr, and this state was maintained during the next heat treatment. When the pressure in the deposition chamber 101 reached 100 Torr, the temperature of the heater 104 was raised to bring the temperature of the support 2 to 250° C., and heat treatment was performed at this temperature for 60 minutes. After the heat treatment, the electrophotographic image forming member created in this manner is transferred to the gate valve 136, main valve 125, valve 13.
0, the flow rate control valve 132 and the valve 135 were closed, and the valve 126 was opened instead to break the vacuum in the deposition chamber 101 and take it out to the outside. Corona discharge was applied to the photoconductive layer surface of this electrophotographic image forming member in the dark with a power supply voltage of 5500 V, and then
Image exposure was performed with an exposure amount of 15 lux sec to form an electrostatic image, and the electrostatic image was developed with charged toner using the cascade method and transferred and fixed onto transfer paper, resulting in an extremely clear image with high resolution. Image obtained. When this image forming process was repeated on the electrophotographic image forming member and the durability of the electrophotographic image forming member was tested, the image obtained on the 100,000th sheet of transfer paper was also of extremely good quality. There is no difference in comparison with the image on the first sheet of transfer paper, and this electrophotographic image forming member has excellent corona ion resistance, abrasion resistance, cleaning properties, etc., and is extremely durable. This has been proven. Note that blade cleaning was adopted as the cleaning method, and the blade was molded from urethane rubber. Example 10 The temperature of the core surrounded by the auxiliary heating furnace 138 is set to 250°C, the filling gas of the heat treatment atmosphere forming gas cylinder 129 is set to NO ₂ , and when introducing gas into the heat treatment chamber, the flow rate adjustment valve 132 is set to 250°C. A coil 134 provided in the gas introduction pipe path between the valve 135 and the valve 135 is energized by a high frequency power source 133 to remove NO ₂
The a--
After forming a Si layer, the heat treatment chamber 127 is heated to 250°C.
After heat treatment for 30 minutes at a temperature of
The vacuum inside 7 was broken and it was taken out to the outside. On this electrophotographic image forming member, corona discharge was applied to the surface of the a-Si photoconductive layer in the dark at a power supply voltage of 5500, and then image exposure was performed at an exposure amount of 15 lux·sec to form an electrostatic image. When this electrostatic image was developed with toner charged by the cascade method and transferred and fixed onto transfer paper, an extremely clear image with high resolution was obtained. Example 11 An a-Si layer with a thickness of 20 μm was formed on an aluminum support in the same manner as in Example 10, except that the annealing atmosphere forming gas was N ₂ and the heat treatment time was 80 minutes. was formed and heat-treated in the same manner to obtain an electrophotographic image forming member. When an image was formed on a transfer paper using this electrophotographic image forming member under the same conditions and procedures as in Example 10, an extremely clear image was obtained. Example 12 Similar to Example 1, using the apparatus shown in FIG.
An electrophotographic imaging member was prepared as follows,
Image formation processing was performed to produce an image. Prepare an aluminum support with a thickness of 1 mm and a size of 34 cm x 27 cm, which has been surface-treated with a 1% NaOH solution, thoroughly washed with water, dried, and cleaned, and placed inside the glow discharge deposition chamber 101. It was firmly fixed at a predetermined position of the fixing member 103 located at a predetermined position. Next, the main valve 125 was fully opened to exhaust the air in the deposition chamber 101, resulting in a vacuum level of approximately 5×10 ⁻⁵ Torr. Then, ignite the heater 104,
The aluminum support was uniformly heated to 50°C and maintained at this temperature. After that, the auxiliary valve 12
4 fully open, then open the valve 20 of the cylinder 108.
0. After fully opening the valve 121 of the cylinder 109,
Gradually open the flow control valves 116 and 117 to supply Ar gas from the cylinder 108 and the cylinder 109.
Then, SiH ₄ gas was introduced into the deposition chamber 101. At this time, the main valve 125 is adjusted so that the deposition chamber 10
The degree of vacuum inside 1 was maintained at approximately 0.07 Torr. Also, in this case, the flow meters 112 and 1
While watching 13, flow control valves 116 and 1
17 was adjusted so that the flow rate of SiH ₄ gas was 10 Vol% of the flow rate of Ar gas. Next, the valve 122 of the cylinder 110 is fully opened, and then the flow rate control valve 118 is gradually opened to control the flow rate to 5×10 ^-4 vol% of the flow rate of SiH ₄ gas, while the inside of the deposition chamber 101 is controlled. B ₂ H ₆ gas was introduced into the solution. At this time as well, the main valve 125 was adjusted to maintain the degree of vacuum in the deposition chamber 101 at 0.07 Torr. Subsequently, the switch of the high frequency power source 105 was turned on, and a high frequency power of 13.56 MHz was applied to the electrodes 106 and 107 to generate a glow discharge inside the deposition chamber 101, resulting in an input power of 100 W. An a-Si layer was grown on the support 2 under these conditions, and the same conditions were maintained for 15 hours to form an a-Si (containing H) layer with a thickness of about 16 μm. After that, the deposition chamber 1
While creating a vacuum inside 01, turn on the high frequency power supply 105.
The glow discharge is stopped as the OFF state, and the flow rate adjustment valves 116, 117, 118, the valves 120, 121, 123, and the auxiliary valve 124 are
is closed and the pressure inside the deposition chamber 101 is reduced to approximately 1×
The vacuum was maintained at 10 ^-5 Torr for 10 minutes.
At this time, the temperature of the support was maintained at the temperature at the time of layer formation. During this time, the valve 14 inside the heat treatment chamber 127
1 was opened to exhaust air and create a vacuum of approximately 1×10 ^-5 Torr. Thereafter, by opening the gate valve 136 and rotating the rotary rollers 139 and 140, the support 10 on which a-Si has been deposited is placed in the heat treatment chamber 127, which has been heated to 250° C. by the heating furnace 128.
2 was moved and the gate valve 136 was closed. Immediately fully open the valves 130 and 135, then gradually open the flow control valve 132 and adjust the valve 141 while introducing O ₂ gas from the cylinder 129 to bring the internal pressure of the heat treatment chamber 127 to approximately 100 Torr, and maintain this state. This was maintained during the next heat treatment. In this manner, heat treatment was performed at 250°C for 30 minutes. After the electrophotographic image forming member created in this way is finished with heat treatment, it is transferred to the support body 102 by a rotating roller 140.
Take out the main valve 141, the valve 130, the flow rate adjustment valve 132, and move it toward the lid 137.
Close valve 135 and replace leak valve 142
was opened to break the vacuum inside the heat treatment chamber 127 and taken out to the outside. This electrophotographic image forming member was subjected to corona discharge with a power supply voltage of 5500 V in the dark.
Image exposure is performed on the surface of the system photoconductive layer at an exposure amount of 15 lux/sec to form an electrostatic image, and the electrostatic image is developed with charged toner by the cascade method to be transferred and fixed onto transfer paper. As a result, extremely clear images with high resolution were obtained. When this image forming process was repeated on the electrophotographic image forming member and the durability of the electrophotographic image forming member was tested, the image obtained on the 100,000th sheet of transfer paper was also extremely poor. It is of good quality and there is no difference compared to the image on the first sheet of transfer paper.
This electrophotographic imaging member has corona ion resistance,
It has been demonstrated that it has excellent abrasion resistance, cleanability, etc., and is extremely durable. Note that blade cleaning was adopted as the cleaning method, and the blade was molded from urethane rubber. Next, the above electrophotographic image forming member was subjected to corona discharge at a power supply voltage of 6000 V in the dark, and then imagewise exposed at an exposure amount of 15 lux·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 image was obtained. From this result and the previous results, it was found that the image forming member obtained in this example had no dependence on charging polarity and had the characteristics of an bipolar photoreceptor. Example 13 In Example 12, an aluminum support was prepared in the same manner as in Example 11, except that the flow rate of B ₂ H ₆ gas was adjusted to be 5 × 10 ^-3 vol% of the flow rate of SiH ₄ gas. An a-Si layer having a thickness of 20 μm was formed thereon, and heat treatment was performed in the same manner to obtain an electrophotographic image forming member. Regarding this electrophotographic image forming member, an image was formed on a transfer paper under the same conditions and procedures as in Example 11. The image quality was excellent and extremely clear. Example 14 Similarly to Example 1, using the apparatus shown in FIG.
An electrophotographic imaging member was prepared as follows,
Image formation processing was performed to produce an image. An aluminum support with a thickness of 1 mm and a size of 34 cm x 27 cm, which had been surface-treated with a 1% Na ₂ OH solution, thoroughly washed with water, and dried to clean the surface, was prepared and placed in the glow discharge deposition chamber 101. It was firmly fixed at a predetermined position of a fixing member 103 located at a predetermined position inside. Next, the main valve 125 was fully opened to exhaust the air in the deposition chamber 101, resulting in a vacuum level of approximately 5×10 ⁻⁵ Torr. Then, ignite the heater 104,
The aluminum support was uniformly heated to 50°C and maintained at this temperature. After that, the auxiliary valve 12
4 fully open, then open the valve 20 of the cylinder 108.
0. After fully opening the valve 121 of the cylinder 109,
Gradually open the flow control valves 116 and 117 to supply Ar gas from the cylinder 108 and the cylinder 109.
Then, SiH ₄ gas was introduced into the deposition chamber 101. At this time, the main valve 125 is adjusted so that the deposition chamber 10
The degree of vacuum inside 1 was maintained at approximately 0.07 Torr. Also, in this case, the flow meters 112 and 1
While watching 13, flow control valves 116 and 1
17 was adjusted so that the flow rate of SiH ₄ gas was 10 vol% of the flow rate of Ar gas. Next, the valve 123 of the cylinder 111 is fully opened, and then the flow rate control valve 119 is gradually opened to control the flow rate to a flow rate of 5×10 ^-3 vol% of SiH ₄ gas, while injecting the SiH 4 gas into the deposition chamber 101. _{B2H6 gas} was introduced. At this time as well, the main valve 125 was adjusted to maintain the degree of vacuum in the deposition chamber 101 at 0.75 Torr. Subsequently, the switch of the high frequency power supply 105 was turned on, and a high frequency power of 13.56 MHz was applied to the electrodes 106 and 107 to generate a glow discharge inside the deposition chamber 101, resulting in an input power of 100 W. After growing an a-Si layer on the support 102 under these conditions and maintaining the same conditions for 15 hours to form an a-Si (containing H) layer with a thickness of about 16μ, the auxiliary valve 124,
The flow control valves 116, 117, and 119 were all closed, and the inside of the deposition chamber 101 was once brought into a vacuum state to 5×10 ⁻⁵ Torr. Next, SiH ₄ gas and Ar gas are again flowed under the same conditions as above, and the inside of the deposition chamber 101 is again
After reaching 0.07 Torr, fully open the valve 122 of the PH ₃ cylinder 110, and then adjust the flow rate adjustment valve 118 to read the flow rate to 1.0 Torr of SiH ₄ gas.
The mixture was mixed and flowed into the deposition chamber 101 so as to have a concentration of ×10 ^-5 vol%. After the gas inflow stabilizes, the high frequency power source 105 is turned on to start glow discharge, and after continuing for 45 minutes, the high frequency power source 105 is turned on.
The glow discharge is stopped in the OFF state, and the flow control valves 116, 117, 118, valves 120, 121, 122, and auxiliary valve 124 are closed, and the pressure inside the deposition chamber 101 is set to approximately 1×10 ^-5 Torr, and the vacuum is maintained for 10 minutes. I kept it to a certain degree. At this time, the temperature of the support was maintained at the temperature at the time of layer formation. Thereafter, heat treatment was subsequently performed under the same procedure as in Example 11 to obtain an electrophotographic image forming member having a PN junction. This electrophotographic image forming member was subjected to corona discharge on the surface of the photoconductive layer in the dark with a power supply voltage of 6000 V, and then subjected to image exposure at an exposure amount of 15 lux·sec to form an electrostatic image. When the image was developed with toner charged by the cascade method and transferred and fixed onto transfer paper, an extremely clear image with high resolution was obtained. Example 15 Using the apparatus shown in FIG. 2, an electrophotographic image forming member was prepared in the following manner and subjected to image forming processing to produce an image. An aluminum support with a thickness of 1 mm and a size of 34 cm x 27 cm, whose surface was treated with a 1% NaOH solution, thoroughly washed with water, and dried to clean the surface, was prepared and placed in a predetermined location in the deposition chamber 201. The fixing member 203 was firmly fixed at a predetermined position. In this case, the support was approximately 8.5 cm away from the polycrystalline silicon target 205 with a purity of 5 nines. Next, the air in the deposition chamber 201 is exhausted, and about 1×
The vacuum level was set to 10 ^-6 Torr. Then heater 2
04 was ignited to uniformly heat the support to 50° C. and maintain this temperature. Then auxiliary valve 2
24, and then open valve 2 of cylinder 209.
13, gradually open the flow rate adjustment valve 221 and adjust it with the main valve 225, supplying H ₂ gas from the cylinder 209 so that the degree of vacuum in the deposition chamber 201 becomes 5.5×10 ^-4 Torr. Deposition chamber 20
It was introduced within 1. Next, after fully opening the valve 212, the flow rate regulating valve 220 is gradually opened while watching the flow meter 216 until the degree of vacuum in the deposition chamber 201 is 5x.
Ar gas is introduced into the deposition chamber 201 at a temperature of 10 ^-3 Torr.
introduced within. After that, the switch of the high frequency power supply 207 is turned on, and a high frequency voltage of 13.56 MHz and 1 KV is applied between the aluminum support and the polycrystalline silicon target 205 to cause a discharge, thereby forming an a-Si layer on the aluminum support. I started it and ran it continuously for 30 hours. The thickness of the resulting a-Si layer was 20 μm. Thereafter, while continuing to evacuate the deposition chamber 201, the high frequency power supply 207 is turned off to stop sputtering, and the flow rate adjustment valve 2
20, 221, valves 212, 213, and auxiliary valve 224 to reduce the pressure in the deposition chamber 201 to about 1
The vacuum was kept at x10 ^-5 Torr for 10 minutes.
At this time, the temperature of the support was maintained at the temperature at the time of layer formation. After that, valve 215, auxiliary valve 22
4, then gradually open the flow control valve 223, and while adjusting the main valve 225, introduce O ₂ gas from the valve 211 to bring the internal pressure of the deposition chamber 201 to about 100 Torr. It was maintained during the heat treatment. When the pressure inside the deposition chamber 201 reaches 100 Torr, the temperature of the heater 204 is increased to bring the temperature of the support to 250 Torr.
℃, and heat treatment was performed at this temperature for 60 minutes. After the electrophotographic image forming member created in this way is heat-treated, the main valve 225, the valve 215, the flow rate adjustment valve 223, the auxiliary valve 22
4 and open the valve 226 instead to open the deposition chamber 2.
The vacuum inside 01 was broken and it was taken out to the outside. The electrophotographic image forming member thus prepared was subjected to corona discharge in the dark at a power supply voltage of 5500 V, and then imagewise exposed at a light intensity of 15 lux·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 16 Using the apparatus shown in FIG. 2, an A-Si layer was formed on an aluminum support in exactly the same manner as in Example 15. Thereafter, this sample was taken out of the deposition chamber 201, the take-out lid 137 of the apparatus shown in FIG. 1 was removed, and the sample was supported on a rotating roller. Next, take out lid 137
Close the main valve 141 and open the heat treatment chamber 12.
The air in the heat treatment chamber 1 is evacuated to create a vacuum level of approximately 1×10 ^-5 Torr, and the heating furnace 128 is turned on.
The temperature inside No. 27 was raised to 250°C and kept constant. Thereafter, the valves 130 and 135 are fully opened, and then the flow rate adjustment valve 132 is gradually opened, and while adjusting the main valve 141, O ₂ gas is introduced from the cylinder 129 to bring the internal pressure of the heat treatment chamber 127 to about 100 Torr.
And so. When the heat treatment conditions became constant as described above, the sample was moved to the position indicated by the dotted line using a rotating roller and heat treated for 60 minutes. After the electrophotographic image forming member produced in this way is heat-treated, the support body 102 is taken out again by the rotating roller 140 and moved toward the lid 137.
30, the flow control valve 132 and the valve 135 were closed, and the leak valve 142 was opened instead to break the vacuum in the heat treatment chamber 127 and take it out to the outside. This electrophotographic image forming member is supplied with a power supply voltage in the dark.
Corona discharge is applied to the surface of the photoconductive layer at 5500V, and then image exposure is performed at an exposure amount of 15lux・sec to form an electrostatic image, which is developed and transferred with toner charged by the cascade method. When transferred and fixed onto paper, an extremely clear image with high resolution was obtained. When this image forming process was repeated on the electrophotographic image forming member and the durability of the electrophotographic image forming member was tested, the image obtained on the 100,000th sheet of transfer paper was also extremely poor. It is of good quality and there is no difference compared to the image on the first sheet of transfer paper.
This electrophotographic imaging member has corona ion resistance,
It has been demonstrated that it has excellent abrasion resistance, cleanability, etc., and is extremely durable. Note that blade cleaning was adopted as the cleaning method, and the blade was molded from urethane rubber.

[Brief explanation of the drawing]

FIG. 1 is a schematic explanatory diagram showing an example of an apparatus that embodies the manufacturing method of the present invention, and FIG. 2 is an example of an apparatus for manufacturing a photoconductive member according to the present invention by a sputtering method. FIG. 101...Deposition chamber, 102...Support, 103
...Fixing member, 104...Heater, 105...
High frequency power supply, 108-111...Cylinder, 116
~119...Flow rate adjustment valve, 120~123...
... Valve, 127 ... Heat treatment chamber, 128 ... Heating furnace, 133 ... High frequency power supply, 137 ... Takeout lid,
138...Auxiliary heating furnace.

Claims (1)

[Scope of Claims] 1. The amorphous silicon layer formed on the support contains at least one of oxygen, nitrogen, and a compound containing an oxygen atom or a nitrogen atom. 1. A method for producing an amorphous photoconductive member, which comprises performing heat treatment in an atmosphere containing at least one of the following. 2. The method for manufacturing an amorphous photoconductive member according to claim 1, wherein the heat treatment is performed at a temperature of 100°C or higher. 3. The method of manufacturing an amorphous photoconductive member according to claim 1, wherein the activation is plasma formation. 4. The method for manufacturing an amorphous photoconductive member according to claim 1, wherein the activation is radicalization. 5 (a) A desired gas is introduced into a deposition chamber that can be reduced in pressure to achieve a desired internal pressure, and a discharge is generated in a space in the deposition chamber where at least one of silicon and a silicon compound exists to generate gas plasma. forming an atmosphere; (b) depositing amorphous silicon on a support that has been placed in the deposition chamber in advance and maintained within a temperature range for layer formation to form an amorphous silicon layer to a desired thickness; (c) The amorphous silicon layer on the support formed in step (b) is heated with oxygen, nitrogen, and
heat treatment in an atmosphere containing at least one of a compound containing an oxygen atom or a nitrogen atom, or containing at least one activated compound thereof; A method for manufacturing an amorphous photoconductive member. 6. The method for manufacturing an amorphous photoconductive member according to claim 5, wherein the upper limit of the temperature range for forming the layer is 100°C or less. 7. The method for producing an amorphous photoconductive member according to claim 5, wherein the heat treatment is performed at a temperature of 100°C or higher. 8. The method for manufacturing an amorphous photoconductive member according to claim 5, wherein the activation is plasma formation. 9. The method for manufacturing an amorphous photoconductive member according to claim 5, wherein the activation is radicalization.