JPS6215856B2 - - 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, it must be non-polluting to the human body during manufacturing and use, and it must also have no afterimage in the image pickup tube. Characteristics such as being able to easily control within a predetermined time are required. Especially,
In the case of an electrophotographic image forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the pollution-free nature during use is an important point. However, it is a conventional photoconductive material that constitutes the photoconductive layer of a commercially available image pickup tube.
Inorganic photoconductive materials such as PbO, Se-As-Te, CdSe, Sb ₂ S ₃ , Se, CdS, ZnO, etc., which are photoconductive materials constituting the photoconductive layer of electrophotographic image forming members, and poly-N It is difficult to assert that organic photoconductive materials (OPC) such as vinylcarbazole (PVK) and trinitrofluorenone (TNF) necessarily satisfy all of the above conditions at 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 directly rubbed during cleaning and other treatments, 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 the Se-based photoconductive layer is repeatedly exposed to corona radiation many times, 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. Alternatively, if the surface of the photoconductive layer is exposed, when visualizing (developing) an electrostatic image,
When using a liquid developer, it is required to have excellent solvent resistance (liquid development resistance) because it comes into contact with the solvent, but Se-based photoconductive layers do not necessarily satisfy this requirement. It is difficult to say with certainty that it is. 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, in electrophotographic imaging members that use ZnO, CdS, etc. as photoconductive layer constituent materials, the photoconductive layer has photoconductive material particles such as ZnO or CdS 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, dipping 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 the photoconductive layer material and a resin binder, and the photoconductive material particles are uniformly dispersed in the resin binder. Due to the specific nature of the photoconductive layer that must be formed, there are many parameters that determine the electrical and photoconductive properties as well as the physical and chemical properties of the photoconductive layer.
Therefore, unless these parameters are precisely adjusted, a photoconductive layer having desired 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 the carrier solvent due to the capillary phenomenon, 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 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 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 optical fatigue.
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 attracted attention, PVK, TNK, 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 has drawbacks such as lacking moisture resistance, corona ion resistance, and cleaning properties, and low photosensitivity, and the spectral sensitivity range in the visible light region is narrow and biased toward short wavelengths. , it is used only 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).
) and amorphous germanium (hereinafter abbreviated as a-Ge). By the way, in the early stages of development, a-Si films and a-Ge films exhibit various electrical and optical properties, which are difficult to reproduce, as their structures depend on the manufacturing method and manufacturing conditions. I had a big problem with my sexuality. 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, n control was impossible in amorphous.
In early 1976, it was reported that a p-n junction could be realized for the first time in amorphous a-Si (Applied Physics Letter; Vol. 28, No. 2,
15 January 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
~10 ⁸ Ω・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. This problem of dark resistance can be said similarly to a-Ge. In addition ^, previous reports on a-Si films indicate that increasing the dark resistance decreases the photosensitivity. In this respect as well, conventional a-Si films could not be used as photoconductive layers for electrophotographic image forming members, image pickup tubes, and the like. Therefore, a method for producing a photoconductive layer having sufficient dark resistance and photosensitivity to be applied as a photoconductive layer for electrophotographic image forming members, image pickup tubes, etc. is needed, taking into account reproducibility and productivity. needs to be developed. Incidentally, the a-Si layer and the a-Ge layer are generally formed on a suitable support by a deposition method that utilizes a discharge phenomenon such as a glow discharge method or a sputtering method. When forming an a-Si or a-Ge layer by such a deposition method, various reports and studies have shown that the dark resistance and photosensitivity of the formed layer change depending on the temperature of the support during layer formation. As shown in the literature. That is, for example, in the case of an a-Si layer, the support temperature is
By forming layers while maintaining the temperature at a high temperature of about 300°C, it is possible to increase the signal-to-noise ratio, which is one of the electrical characteristics. However, the layer growth rate of a-Si is, for example, Se
It is extremely difficult to maintain a constant high temperature with high precision until the layer thickness required for the photoconductive layer of electrophotographic image forming members, image pickup tubes, etc. is reached. . Furthermore, in the case of a photoconductive layer of an electrophotographic image forming member, the total light-receiving surface requires a large area, for example, A4 size or B4 size or more, even in normal cases. With the current technology, it is extremely difficult to control the temperature in order to uniformly maintain the high temperature state shown above over a large area until the layer formation is completed. However, even when changing the temperature of the support, it is difficult to control the temperature change rate over such a large area so as not to vary depending on the 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, making it difficult not only to achieve uniform layer thickness over a large area, but also to achieve uniform electrical and optical properties required for the photoconductive layer. I can't even do that. The present invention has been made in view of the above-mentioned points, and from the viewpoint of applying a-Si and a-Ge to photoconductive layers of electrophotographic image forming members, image pickup tubes, etc. As a result of intensive research and study, we found that an amorphous semiconductor layer (hereinafter referred to as an a-semiconductor layer) formed using Si and Ge as a matrix using a predetermined method was developed at a specific temperature (Ta) in a specific atmosphere. The present invention is mainly based on the discovery that heat treatment results in a photoconductive layer having the excellent properties desired in the present invention. Furthermore, the present invention provides 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. Even if the photoconductive layer is extremely poor and cannot be used conventionally, if heat treatment is performed at a certain temperature (Ta) and atmosphere after layer formation,
The point is that it has been found that the required electrical characteristics are 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 stable electrical and optical properties at all times, extremely high sensitivity, extremely long 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. An intended object of the present invention is to provide an a-semiconductor layer formed on a support using Si and Ge as a matrix, containing at least one of oxygen, nitrogen, and a compound containing an oxygen atom or a nitrogen atom. This is accomplished by manufacturing an amorphous photoconductive member (hereinafter referred to as an a-photoconductive member) by heat treatment in an atmosphere containing at least one of the above-mentioned activated materials. Further, an intended object of the present invention is to (a) introduce a desired gas into a deposition chamber capable of reducing the pressure to achieve a desired internal pressure, and at least one of silicon and silicon compounds and germanium and germanium in the deposition chamber; (b) forming a gas plasma atmosphere by generating an electric discharge in a space in which at least one of the compounds is present; (b) on a support previously placed in the deposition chamber and maintained within the temperature range for layer formation (c) maintaining the gas plasma atmosphere for a sufficient time to form an amorphous semiconductor layer to a desired thickness by depositing an amorphous semiconductor on the support; The semiconductor layer is heat-treated in an atmosphere containing at least one of oxygen, nitrogen, and a compound containing an oxygen atom or a nitrogen atom, or an activated one thereof. This is effectively achieved by a method for manufacturing an amorphous photoconductive member characterized by including the following. In the present invention, a-
By subjecting the semiconductor layer to heat treatment described in detail below, an amorphous photoconductive layer (hereinafter referred to as a
- photoconductive layer), but a
-Support temperature when forming the semiconductor layer on the support
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-semiconducting layer deteriorate, but the physical properties of the layer formed at such a temperature will be lower than the photoconductivity of electrophotographic image forming members, image pickup tubes, etc. The physical properties of the layer will fall outside the range required for the layer, making it unsuitable for use.Also, if the temperature is too far from T _R , it will require control for cooling, so In some cases, it is better to set it as T _R.
Incidentally, T _R in the present invention refers to 20 to 25°C. a - After forming the semiconductor layer, the temperature Ta for heat treatment is:
The desired electrical and optical properties that can achieve the purpose of the present invention, and further electrophotographic properties when applied to electrophotography, are selected as appropriate within the range. ℃ or higher, preferably 150℃
It is desirable that the amount is more than that. The upper limit of Ta is set at a temperature at which the formed a-photoconductive layer does not crystallize to the extent that it adversely affects the desired properties, usually 450°C, preferably 400°C. It is desirable to In particular, it is optimal to set Ta in a temperature range of 200 to 350°C. In the present invention, the heat treatment time is as follows:
Although it varies depending on the thickness and area of the formed layer, the type of support on which the layer is formed, etc., it is generally good to set it to 15 to 180 minutes. In the present invention, the formed a-semiconductor layer is formed of an annealing atmosphere-forming material or/and an activated version thereof as described below in order to undergo a post-layer heat treatment. exposed to a harsh atmosphere. In order to heat-treat the a-semiconductor layer in the above atmosphere, the support on which the a-semiconductor layer is formed is heated.
The heat treatment may be carried out by heating to Ta, or the temperature of the atmosphere in which the a-semiconductor layer is placed (ambient temperature) may be set to Ta for heat treatment, or the temperature of the support may be and the ambient temperature.
You can also go on Ta. In the present invention, substances that form an atmosphere when heat-treating an a-semiconductor layer formed on a desired support with a desired layer thickness and area (hereinafter referred to as an annealing atmosphere forming substance) include: Oxygen, nitrogen, oxygen atoms or compounds containing nitrogen atoms, air,
Alternatively, a mixture thereof can be used. In the present invention, this annealing atmosphere-forming substance may be left in its normal state as a gas, or may be converted into plasma or radicals.
a- After completing the semiconductor layer formation, without breaking the vacuum,
a - It may be introduced into the same deposition chamber as that for forming the semiconductor layer and subjected to subsequent heat treatment (continuous method No. 1), or the deposition chamber may be designed so that the contents inside the chamber can be transferred without breaking the vacuum. It is also possible to continue heat treatment by introducing it into the heat treatment chamber where it is currently being processed (continuous method No. 2).
After forming the a-semiconductor layer, the a-semiconductor layer is once taken out of the deposition chamber into the atmosphere and then introduced again into a heat treatment chamber provided separately from the deposition chamber for heat treatment. Continuous method) is also good. However, in order to further improve mass productivity and uniform characteristics of the formed a-semiconductor layer, continuous method No. 2 is the most preferred of the above three heat treatment methods. The annealing atmosphere forming substance containing oxygen atoms or nitrogen atoms includes a formed during heat treatment.
- Impurities unnecessary for achieving the purpose of the present invention are incorporated into the semiconductor layer, or chemically or physically formed a- Almost any material can be used as long as it does not deteriorate the semiconductor layer. obtain. As such an annealing 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), and suboxide. Nitrogen (N ₂ O), nitrogen sesquioxide (N ₂ O ₃ ), nitrogen tetroxide (N ₂ O ₄ ), nitrogen dioxide (NO ₂ ), nitrogen pentoxide (N ₂ O ₅ ), ammonia (NH ₃ ), etc., and many others are effective. 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-semiconductor layer (a-photoconductive layer) has uniform electrical and optical properties over a large area, and the uniformity is does not change over time, and surprisingly, when applied to electrophotographic imaging members, it has excellent electrostatic properties, corona ion resistance, solvent resistance, abrasion resistance, cleaning properties, etc. Therefore, there is almost no deterioration of electrophotographic characteristics 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, Nb, Ta, V, Ti,
A conductive support made of metals such as Pt, Pd, or alloys thereof, or a conductive support on which these metals are vapor-deposited, or a synthetic resin film that exhibits heat resistance, at least heat resistance in Ta. or a sheet, or an electrically insulating support such as glass or ceramic, etc. are effective examples. The support is subjected to a series of cleaning treatments before the a-semiconductor is deposited thereon. In such cleaning treatments, typically, for example, a metallic support is contacted with an alkaline or acidic solution that effectively cleans the surface by etching. The support is then dried in a clean atmosphere and, without any further preparatory treatment, placed in position in the deposition chamber of an apparatus for depositing a-semiconductors onto the support using electrical discharge phenomena. In the case of electrically insulating supports, if necessary,
Its surface is conductively treated. For example, if it is glass, its surface is conductive treated with In ₂ O ₃ or SnO ₂ , or if it is a synthetic resin film such as polyimide film, it can be 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 and a-Ge on a support installed in a deposition chamber to form an a-semiconductor layer with a desired thickness, first, a predetermined pressure is set in the deposition chamber, e.g. After reducing the pressure to about 1 × 10 ^-3 to 1 × 10 ^-8 Torr, the support is maintained at a temperature Ts, and a predetermined gas is introduced into the deposition chamber to cause a discharge phenomenon, which causes a discharge in silicon and silicon compounds. A gas plasma atmosphere is formed in the space within the deposition chamber where at least one of germanium and germanium and a germanium compound are present, and the gas plasma atmosphere is maintained for a sufficient period of time until a desired layer thickness is achieved. . Deposition methods that utilize a discharge phenomenon include a glow discharge method, a sputtering method, an ion plating method, and the like, and the a-semiconductor layer is formed on a support by such a deposition method. In the present invention, an AC or DC power source is used to generate an effective discharge phenomenon in the deposition chamber to form a desired plasma atmosphere. The voltage is regulated to 300-1500V, and the input power is usually
It is good to set it as 0.1-300W, suitably 0.5-100W. Further, in the case of AC, the frequency is usually 0.2 to 30 MHz, preferably 5 to 20 MHz. In the present invention, the a-semiconductor layer to be heat-treated is formed of one of the following types of a-semiconductors, or at least two types are selected, and different types are bonded together. Obtained by layering. n-type...contains only a donor;
Or one that contains both a donor and an acceptor and has a high donor concentration (Nd). P-type: contains only acceptors. Or one that contains both a donor and an acceptor and has a high concentration of acceptor (Na). Type i...NaNdO or NaNd. The a-semiconductor layer of type ~ as a layer constituting the photoconductive layer in the present invention is not contaminated with n-type impurities or , a p-type impurity, or both impurities are doped into the a-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 n-type) a-semiconductor layer can be formed from a stronger p-type a-semiconductor layer. The a-semiconductor layer of type ~ is formed by a glow discharge method, 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-photoconductive member having desired characteristics, and it is possible to introduce impurities into the a-semiconductor layer formed to control the type of ~. Alternatively, the glow discharge method is preferably employed because of its advantages such as the ability to introduce group V impurities 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 semiconductor layer may also be formed. The formed a-semiconductor layer has desired characteristics, and its dark resistance and photoelectric gain are controlled by containing H during its formation. Here, "H is contained in the a-semiconductor layer" means "a state in which H is combined with Si or Ge", "H
It means a state in which H ₂ is ionized and incorporated into the layer, or a state in which H 2 is incorporated into the layer, or a combination thereof. a- H is introduced into the semiconductor layer in the form of compounds such as SiH ₄ , Si ₂ H ₆ , GeH ₄ or H ₂ into the manufacturing equipment system when forming the layer, and by gas discharge,
These compounds or H ₂ are decomposed and incorporated into the a-semiconductor layer as the layer grows. According to the findings of the present inventors, the H content in the a-semiconductor 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 it 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. The inclusion of H in the a-photoconductive layer is, for example, in the glow discharge method, when the starting material for forming the a-semiconductor is a silicon hydride such as SiH ₄ or Si ₂ H ₆ .
Since we use hydride germane such as _GeH4 ,
Hydrogens such as SiH ₄ , Si ₂ H ₆ , GeH ₄ decompose and form a-
When a semiconductor layer is formed, H is automatically contained in the layer, but in order to further efficiently contain H into the layer, glow discharge is performed when forming the a-semiconductor layer. All you have to do is introduce _H2 gas into the equipment system. In the case of the sputtering method, sputtering is performed in an atmosphere of an inert gas such as Ar or a mixed gas based on this gas, with two targets of Si and Ge, or a mixed system (Si+Ge) as a target. When performing this, H ₂ gas is introduced or silicon hydride gas such as SiH ₄ or Si ₂ H ₆ is used.
A germanium hydride gas such as GeH ₄ or a gas such as B ₂ H ₆ or PH ₃ which also serves as impurity doping may be introduced. The a-semiconductor layer can be controlled to the above-mentioned types by doping with impurities during manufacturing. In order to make the a-semiconductor layer P-type, suitable impurities to be doped into the a-semiconductor layer include elements of group A of the periodic table, such as B, Al, Ga, In, and Tl. In the case of n-type, elements of group A of the periodic table, such as N, P,
Preferred examples include As, Sb, and Bi. The amount of impurity doped into the a-semiconductor layer is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities in group A of the periodic table, it is usually 10 ^-6 to 10 ^-3 atomic%, preferably 10 ^-5 ~
10 ^-4 atomic%, in the case of impurities of group A of the periodic table, usually 10 ^-8 to 10 ^-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-semiconductor layer differs depending on the manufacturing method adopted when forming the a-semiconductor layer, and specifically, the methods for doping these impurities into the a-semiconductor layer are as follows: This will be explained in detail in . a-The thickness of the photoconductive layer depends on the desired electrical and optical properties, electrophotographic properties if applied to electrophotography, and usage conditions, such as whether flexibility is required. Although it is determined appropriately depending on the
It is desirable that the thickness be 70μ, optimally 10 to 50μ. 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 producing 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 member 102 is installed on the lower side of the support member 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 gas introduction pipe is connected to the upper end of the deposition chamber 101, and gas cylinders 108, 1
09, 110, 111, and 112, the gas in each cylinder is introduced into the deposition chamber 101 when necessary. 113, 114, 115, 11
6 and 117 are flow meters, which are meters for detecting the flow rate of gas, and 118 and 11
9, 120, 121, 122 are flow rate adjustment valves,
Valve 128 is an auxiliary valve. Also, the lower end of the deposition chamber 101 has a main valve 129.
via an exhaust system (not shown). 130 is a valve for breaking the vacuum in the deposition chamber 101. A heat treatment chamber 131, which is a chamber for heat treating the a-semiconductor layer formed in the deposition chamber 101, is connected to the left side of the deposition chamber 101. The deposition chamber 101 and the heat treatment chamber 131 are operated by opening and closing the gate valve 140 without breaking the vacuum.
It is designed so that the contents inside can be moved and can be used as an independent room. 132 is a heating furnace used when heat-treating the a-semiconductor layer in the heat treatment chamber 131, and for example, infrared heating means or heating means with a built-in heater can be used. A gas introduction pipe is connected to an extension of the left end of the heat treatment chamber 131 so that an annealing atmosphere forming substance is introduced into the heat treatment chamber 131 from a cylinder 133 . 134 and 139 are valves, 136 is a flow rate control valve, and 135 is a flow meter. An inductance coil 138 connected to a high frequency power source 137 is wound between the flow control valve 135 and the valve 139 of the gas introduction pipe, and introduces an annealing atmosphere forming substance from the cylinder 133 into the heat treatment chamber 131. When necessary, the atmosphere-forming substance can be activated in advance by turning it into plasma or turning it into radicals. 142 is an auxiliary heating furnace, and the heat treatment chamber 13
This is a means for preheating the annealing atmosphere forming substance introduced into the heat treatment chamber 131 or its activated substance to a predetermined temperature before introducing it into the heat treatment chamber 131. In order to form an a-photoconductive layer with desired characteristics on the support 102 using the glow discharge deposition apparatus shown in FIG.
02 is fixed to the fixing member 103 with the cleaned side facing upward. 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 129 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 128, and then open the valve 123 of the gas cylinder 108 and the gas cylinder 10.
The valves 124 and 125 of Nos. 9 and 110 are each fully opened. The gas cylinder 108 is for dilution gas such as Ar gas, and the gas cylinders 109 and 110 are for a dilution gas such as Ar gas.
- For raw material gas for forming semiconductor layers,
The gas cylinder 109 is made of, for example, SiH ₄ , Si ₂ H ₆ ,
Si ₄ H ₁₀ or a mixture thereof etc. is added to the gas cylinder 1.
10 stores, for example, GeH ₄ and the like. Further, the cylinder 111 and the cylinder 112 are for raw material gases for introducing impurities into the a-semiconductor layer as necessary, and are for PH ₃ , P ₂ H ₄ , B ₂ H ₄ , respectively.
B ₂ H ₆ etc. are stored. Then gas cylinder 1
Flow control valve 11 of 08, 109 and 110
8,119,120, flow meter 113,1
14 and 115, each is gradually opened and a diluent gas such as Ar gas, Ar gas, etc. is introduced into the deposition chamber 101.
And, for example, a of SiH ₄ gas etc. and GeH ₄ gas etc.
-Introduce raw material gas for semiconductor formation. At this time
A diluent gas such as Ar gas is not necessarily required, and only the raw material gases such as SiH ₄ gas and GeH ₄ gas may be introduced. When Ar gas is introduced as a mixture with the raw material gas for forming the a-semiconductor layer, the quantitative ratio is determined according to the requirements, but usually the raw material gas is 10 Vol% with respect to the dilution gas.
This is considered to be the above. Note that a rare gas such as He gas may be used as the diluent gas instead of Ar gas. Inside the deposition chamber 101, cylinders 108, 109, 1
At the point when the gas is introduced from 10, the main valve 129 is adjusted to obtain a predetermined degree of vacuum, usually at the gas pressure when forming the a-semiconductor layer.
Keep at 10 ^-2 to 3 Torr. Next, a capacitance type electrode 106,1 is wound around the outside of the deposition chamber 101.
When a glow discharge is caused in the deposition chamber 101 by applying a high frequency voltage of a predetermined frequency, usually 0.2 to 30 MHz, from the high frequency power source 105 to 07, for example,
SiH ₄ gas and GeH ₄ gas are decomposed and the support 10
A semiconductor consisting of Si and Ge is deposited on 2 and a-
A semiconductor layer is formed. When introducing impurities into the a-semiconductor layer to be formed, an impurity-generating gas may be introduced into the deposition chamber 101 from the cylinder 111 or 112 at the time of forming the a-semiconductor layer. In this case, by appropriately adjusting the flow rate control valve 121 or 122, the amount of gas introduced into the deposition chamber 101 from the cylinder 111 or 112 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-semiconductor layer. Next, after an a-semiconductor layer with a predetermined thickness is formed on the support 102, the high frequency power source 105 is turned off and the valves 118, 119, 120, 128 and, if necessary, the valves 121, 122 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 145 is fully opened and the heat treatment chamber 131 is evacuated to a predetermined degree of vacuum as shown by the arrow B, at the position shown by the dotted line, the gate valve 140 is opened, and the pair of rotating rollers 143 and a series of a plurality of rotating rollers 144, the support body 102
Transfer the a-semiconductor layer formed above. after that,
Gate valve 140 is closed again. In this case, the heat treatment chamber 131 may be heated in advance by the heating furnace 132, or the a-semiconductor layer may be moved from the deposition chamber 101 to the position indicated by the dotted line, and the gate valve 140 may be closed. You may start raising the temperature later. The heat treatment chamber 131 into which the a-semiconductor layer is introduced is
The valves 134 and 139 are fully opened, and while monitoring the flow meter 135, the flow rate adjustment valve 136 is gradually opened to introduce the annealing atmosphere forming substance from inside the cylinder 133, and the flow rate adjustment valve 13 is gradually opened.
6 and the main valve 145 are adjusted to a predetermined internal pressure, and the heat treatment is started. In this case, the internal pressure of the heat treatment chamber 131 may be increased to above atmospheric pressure, or may be reduced to below atmospheric pressure. Next, after the a-semiconductor layer is heat-treated for a predetermined time, the flow control valve 136 and the valve 139 are closed, and the heating furnace 132 is turned off. After that, the support body 102 is moved in the direction of the take-out lid 141 by the rotating roller 144, cooled to a predetermined temperature, the main valve 145 is closed, and the take-out lid 141 is gradually opened using the leak valve 146. The a-photoconductive layer (heat-treated a-semiconductor 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 above it, Si and Ge are placed at a predetermined ratio at a position facing the support 202 with a predetermined interval. A target 205 consisting of is placed on the electrode 206. When using Si target and Ge target, 2
Attach one target to electrode 206 or
Two targets are used, each attached to an electrode provided for each target. Fixing member 203 on which support body 202 is installed
A high frequency voltage is applied between the target 205 and the target 205 by a high frequency power supply 207. Further, in the deposition chamber 201, cylinders 208 and 20 are installed.
9, 210, 211 are valves 212, 21, respectively.
3,214,215, flow meter 216,21
7,218,219, flow rate adjustment valve 220,2
21, 222, 223 are connected via an auxiliary valve 224, and cylinders 208, 209, 21
0.211, 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 deposition chamber 201 and the
It is also possible to provide 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, and activating the annealing atmosphere forming substance before introducing it into the deposition chamber 201. good. 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-semiconductor 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
It is assumed to be 3×10 ^-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 target 205, on which the supporting body 202 is installed, and the generated ions of the atmospheric gas such as Ar ions sputter the Si and Ge of the target 205. An a-semiconductor layer is formed thereon. 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.
- The semiconductor layer can be adjusted to be 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
- Deposition chamber 20 from cylinder 210 during semiconductor layer formation
1 to dope P or B as an impurity into the a-semiconductor layer. In addition, impurities may be introduced into the formed a-semiconductor layer by ion implantation. in this case,
The extremely thin surface layer of the a-semiconductor layer can be easily controlled to have a specific conductivity type. Next, after an a-semiconductor 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 heat-treated a-semiconductor layer (a-photoconductive layer) is cooled to a predetermined temperature (usually room temperature). 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. 34cm x 27cm, 2mm thick
A glass substrate (support 102) having a transparent conductive film of SnO ₂ on its surface is cleaned with a neutral detergent, followed by ultrasonic cleaning, rinsing with running water, pure water cleaning, cleaning with ethyl alcohol and potassium hydroxide, and pure water cleaning. ,
It was thoroughly cleaned using an ultrasonic cleaning process and dried.
In this way, the prepared support 102 is placed on the fixing member 10 at a predetermined position in the glow discharge deposition chamber 101.
3 was firmly fixed in place. Next, the main valve 129 was fully opened to exhaust the air in the deposition chamber 101, resulting in a degree of vacuum of approximately 5×10 ⁻⁵ Torr. Thereafter, the heater 104 was ignited to uniformly heat the support to 50° C., and the temperature was maintained at this temperature. After that, fully open the auxiliary valve 128,
Subsequently, the valve 123 of the cylinder 108 and the cylinder 1
After fully opening the valve 124 of the cylinder 10, gradually open the flow control valves 118 and 119.
Ar gas was introduced into the deposition chamber 101 from a cylinder 109, and SiH ₄ gas was introduced from a cylinder 109. At this time, the main valve 129 is adjusted so that the degree of vacuum in the deposition chamber 101 is approximately
It was maintained at 0.07Torr. Subsequently, _GeH4
Gas (99.999% purity) cylinder 110 valve 1
25 and gradually open the flow rate adjustment valve 120.
The opening of the flow control valve 120 was determined so that the flow meter 115 read 30% of the flow rate of SiH ₄ gas, and the flow rate was stabilized. The internal pressure of the deposition chamber 101 at this time was about 0.05 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-semiconductor layer was grown on the support 102 under these conditions, and the same conditions were maintained for 18 hours to form an a-semiconductor (H-containing) layer having a thickness of about 20 μm. after that,
Subsequently, while drawing a vacuum inside the deposition chamber 101, the high frequency power source 105 is turned off to stop glow discharge, and the flow rate adjustment valves 118 to 120, valves 123 to 125, and auxiliary valve 128 are closed.
The pressure inside the deposition chamber 101 is set to approximately 1×10 ^-5 Torr.
The vacuum 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 145 was also opened in the heat treatment chamber 131 to exhaust the air to create a vacuum of approximately 1×10 ⁻⁵ Torr. After that, the gate valve 140 is opened and the rollers 143, 1 rotate once.
A-semiconductor is deposited on the support 102 at the position shown by the dotted line in the heat treatment chamber 131, which is heated to 250° C. by the heating furnace 132 by rotating the support 102.
was moved, and the gate valve 140 was closed. Immediately fully open the valves 134 and 139, then gradually open the flow control valve 136 and adjust the main valve 145 while introducing O ₂ gas from the cylinder 133 to reduce the internal pressure of the heat treatment chamber 131 to approximately
The temperature was set at 100 Torr, and this state was maintained during the heat treatment. In this manner, heat treatment was performed at a temperature of 250°C for 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 141 by the rotating roller 144, and the valve 145, the valve 134, and the flow rate adjustment valve 13 are removed.
6. Close valve 139 and replace it with leak valve 1
46 was opened to break the vacuum inside the heat treatment chamber 131 and taken out to the outside. In this electrophotographic imaging member,
Corona discharge was performed on the surface of the photoconductive layer 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, which was charged by the cascade method. When the image was developed with toner and transferred and fixed onto transfer 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. As the cleaning method, blade cleaning was used, and the blade was molded from urethane rubber. Example 2 Example 1 except that the conditions shown in Table 1 were used.
An a-semiconductor layer is formed on an aluminum support which has been cleaned in a conventional manner under the same conditions and procedures as in Table 2, followed by a heat treatment for 60 minutes at the temperatures shown in Table 2. The samples were taken out of the chamber 101 to obtain electrophotographic image forming members designated by sample No. s. 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 by the cascade method and transferred and fixed onto transfer paper. Regarding the resulting transferred image. , conducted an evaluation.
The results are shown in Table 2.

【table】

[Table] Evaluation: ◎...Excellent ○...Good △...Practically acceptable ×...Practically not possible Example 3 Normally tested under the same conditions and procedures as in Example 1 except for the conditions shown in Table 3. An a-semiconductor layer was formed on the aluminum support which had been cleaned by the method described above, and then heat treated for 30 minutes at the temperature shown in Table 4, and then taken out of the deposition chamber 101 and sample Nos. Electrophotographic image forming members shown in the following were obtained. In addition, the samples were not subjected to any heat treatment.
An electrophotographic image forming member manufactured under the same conditions as No. s~ was used as a comparison sample. 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 by the cascade method and transferred and fixed onto transfer paper. Regarding the resulting transferred image. , 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-semiconductor layer is formed on an aluminum support which has been cleaned in a conventional manner under the same conditions and procedures as above, and is then heat treated at the temperatures and times shown in Tables 5 and 6. After that, the samples were taken out of the deposition chamber 101 to obtain electrophotographic image forming members designated by sample No. s. Corona discharge was applied to the photoconductive layer surface of these electrophotographic image forming members 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,
The electrostatic image was developed with toner charged by a cascade method, transferred and fixed onto a transfer paper, and the resulting transferred surface image was evaluated. The result is the 6th
Shown in the table.

【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-semiconductor layer is formed on an aluminum support which has been cleaned in a conventional manner under the same conditions and procedures as above, followed by heat treatment at the temperatures and times shown in Tables 7 and 8. After that, the samples were taken out of the deposition chamber 101 to obtain electrophotographic image forming members designated by sample No. s. Corona discharge was applied to the photoconductive layer surface of these electrophotographic image forming members in the dark with a power supply voltage of 5500 V, and then 15 lux・sec
An electrostatic image is formed by performing image exposure at an exposure amount of , 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-semiconductor layer is formed on an aluminum support that has been statically purified in a conventional manner under the same conditions and procedures as above, and then heat treatment is performed at the temperature and time shown in Tables 9 and 10. After that, the samples were taken out of the deposition chamber 101 to obtain electrophotographic image forming members designated by sample No. s. Corona discharge was applied to the photoconductive layer surface of these electrophotographic image forming members 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,
The electrostatic image was developed with toner charged by a cascade method, transferred and fixed onto a transfer paper, and the resulting transferred image was evaluated. The result is the 10th
Shown in the table.

【table】

[Table] Evaluation: ◎...Excellent ○...Good △...Practically acceptable ×...Practically not possible
Example 7 An image forming member was formed under the same conditions and procedures as in Example 1, except that the temperature of the core surrounded by the auxiliary heating furnace 142 was also maintained at 250° C. during the heat treatment. That is, an a-semiconductor layer is formed on an aluminum support which has been cleaned in a conventional manner under the same conditions and procedures as in Example 1, and is then heat-treated in a heat treatment chamber 131 at a temperature of 250° C. for 20 minutes. After performing this, the vacuum inside the heat treatment chamber 131 was broken and the sample 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 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. 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. As the cleaning method, blade cleaning was used, and the blade was molded from urethane rubber. Example 8 The temperature of the core surrounded by the auxiliary heating furnace 142 was maintained at 350°C during the heat treatment, and the heating furnace 132 was not turned on and the same procedure and conditions as in Example 1 were followed except for the heat treatment conditions. An imaging member was formed. That is, an a-semiconductor layer is formed on an aluminum support that has been cleaned in a conventional manner under the same conditions and procedures as in Example 1, and then heated in a heat treatment chamber 13.
1, after heat treatment was performed for 40 minutes at a gas temperature of 350° C., the vacuum in the heat treatment chamber 131 was broken and the material 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 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. 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 in comparison with the image on the first sheet of transfer paper, and this electrophotographic image forming member is extremely durable with excellent corona ion resistance, abrasion resistance, and cleaning properties. It has been proven that there is. Note that blade cleaning was adopted as the cleaning method, and the blade was molded from urethane rubber. Example 9 In the same manner as in Example 1, the apparatus shown in FIG.
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 102 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, and dried to clean the surface, is prepared and placed in a glow discharge deposition chamber. It was firmly fixed at a predetermined position of a fixing member 103 located at a predetermined position within 101. Next, the main valve 129 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 was ignited to uniformly heat the aluminum support 102 to 50° C., and the temperature was maintained at this temperature. After that, the auxiliary valve 128 is fully opened, and then the valve 123 of the cylinder 108 and the valve 124 of the cylinder 109 are fully opened, and then the flow rate adjustment valves 118 and 119 are gradually opened to supply Ar gas from the cylinder 108 to the cylinder 1.
From 09 onwards, SiH ₄ gas was introduced into the deposition chamber 101. At this time, the main valve 129 was adjusted so that the degree of vacuum in the deposition chamber 101 was maintained at approximately 0.07 Torr. Next, add GeH ₄ gas (99.99% purity) to cylinder 1.
10 valves 125 are opened, and the flow rate adjustment valve 12 is opened.
0 was gradually opened, and the opening of the flow rate adjustment valve 120 was determined so that the reading of the flow meter 115 was 30% of the flow rate of SiH ₄ gas, and the opening was stabilized. The internal pressure of the deposition chamber 101 at this time was about 0.05 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-semiconductor layer was grown on the support 102 under these conditions, and the same conditions were maintained for 18 hours to form an a-semiconductor (H-containing) layer having a thickness of about 20 μm. after that,
Subsequently, while drawing a vacuum inside the deposition chamber 101, the high frequency power source 105 is turned off to stop glow discharge, and the flow rate adjustment valves 118 to 120, valves 123 to 125, and auxiliary valve 128 are closed.
The pressure inside the deposition chamber 101 is set to approximately 1×10 ^-5 Torr.
The vacuum 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 140 was opened, and the inside of the heat treatment chamber 131 was evacuated to the same degree of vacuum as the inside of the deposition chamber 101. Next, the valves 134 and 139 are fully opened, and then the flow rate adjustment valve 136 is gradually opened, and while the main valve 129 is adjusted, O ₂ gas is introduced from the cylinder 133 to bring the internal pressure of the deposition chamber 101 to approximately 100 Torr. , and this state was maintained during the next heat treatment. The pressure inside the deposition chamber 101 is
At the point when the temperature reaches 100Torr, heating heater 1
04 to increase the temperature of the support 102.
The temperature was set to 250°C, and heat treatment was performed at this temperature for 60 minutes.
The member having the photoconductive layer created in this way is
After the heat treatment, the gate valve 140, the main valve 129, the valve 134, the flow rate adjustment valve 13
6. Close valve 139 and replace it with valve 146
was opened to break the vacuum in the deposition chamber 101 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 on transfer 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. Example 10 The temperature of the core surrounded by the auxiliary heating furnace 142 is set to 250°C, and the filling gas in the cylinder 133 for annealing atmosphere forming gas is NO ₂
Also, when introducing gas into the heat treatment chamber 131, a coil 138 provided in the gas introduction pipe path between the flow rate adjustment valve 136 and the valve 139 is energized by the high frequency power supply 137 to turn the NO ₂ gas into plasma and enter the heat treatment chamber. An image forming member was formed using the same procedure and conditions as in Example 1, except for the conditions of introduction and heat treatment in the heat treatment chamber 131. That is, an a-semiconductor layer was formed on an aluminum support that had been cleaned in a conventional manner under the same conditions as in Example 1, and then heat-treated at a temperature of 250° C. for 30 minutes in a heat-treating chamber 131. Thereafter, the vacuum inside the heat treatment chamber 131 was broken and the sample 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 image exposure was performed with an exposure amount of 15 lux·sec 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. 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 images obtained on the transfer paper after 100,000 prints were 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. Incidentally, as a cleaning method, a blade cleaning was adopted, and a blade molded from urethane rubber was used. Example 11 An a-semiconductor 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. Then, heat treatment was performed 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 In the same manner as in Example 1, an electrophotographic image forming member was prepared in the following manner using the apparatus shown in FIG. 1, 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, 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 the fixing member 103 located at a predetermined position. Next, the main valve 129 was fully opened to exhaust the air in the deposition chamber 101, resulting in a degree of vacuum 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
8, and then open the valve 12 of the cylinder 108.
3. After fully opening the valve 124 of the cylinder 109,
Gradually open the flow control valves 118 and 119 to supply Ar gas from the cylinder 108 to the cylinder 109.
Then, SiH ₄ gas was introduced into the deposition chamber 101. At this time, the main valve 129 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 113 and 1
14, flow control valves 118 and 1.
19 to adjust the flow rate of SiH ₄ gas to that of Ar gas.
It was set to 10Vol%. Next, add GeH ₄ gas (99.999% purity) to cylinder 1.
10 valves 125 are opened, and the flow rate adjustment valve 12 is opened.
0 gradually, and the reading of flow meter 115 is
The opening of the flow rate adjustment valve 120 was determined to be 30% of the flow rate of SiH ₄ gas, and the flow rate was stabilized. The internal pressure of the deposition chamber 101 at this time was about 0.05 Torr. Next, the valve 126 of the cylinder 111 is fully opened, and then the flow rate adjustment valve 121 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 129 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-semiconductor layer was grown on the support 102 under these conditions, and the same conditions were maintained for 18 hours to form an a-semiconductor (H-containing) layer having a thickness of about 20 μm. after that,
Subsequently, while drawing a vacuum inside the deposition chamber 101, the high frequency power supply 105 is turned off to stop glow discharge, and the flow rate adjustment valves 118 to 121, valves 123 to 126, and auxiliary pulp 128 are closed to reduce the pressure inside the deposition chamber 101. The vacuum level was approximately 1 x 10 ^-5 Torr and maintained at that level 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 145 was also opened in the heat treatment chamber 131 to exhaust the air and create a vacuum of approximately 1×10 ⁻⁵ Torr. After that, the gate valve 140 is opened and the rotating roller 143,
By rotating the heating furnace 144,
The support body 102 on which the a-semiconductor was deposited was moved to the position of the heat treatment chamber 131 whose temperature was raised to 250° C. in Step 2, and the gate valve 140 was closed. Immediately fully open the valves 134 and 139, then gradually open the flow control valve 136 and close the valve 145.
While adjusting the temperature, O ₂ gas was introduced from the cylinder 133 to bring the internal pressure of the heat treatment chamber 131 to about 100 Torr, and this state was maintained during the heat treatment. In this manner, heat treatment was performed at a temperature of 250°C for 30 minutes. After the electrophotographic image forming member produced in this way is heat-treated, the support body 102 is taken out by the rotating roller 144 and moved toward the lid 141, and the main valve 145 is opened.
Valve 134, flow rate adjustment valve 136, valve 1
39 was closed, and the reel valve 146 was opened instead to break the vacuum inside the heat treatment chamber 131 and take it out to the outside. This electrophotographic image forming member was subjected to corona discharge on the surface of the photoconductive layer in the dark at a power supply voltage of 5500 V, and then imagewise exposed 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. 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 electrophotographic image forming member obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar image forming member. 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-semiconductor 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. When an image was formed on a transfer paper using this electrophotographic image forming member under the same conditions and procedures as in Example 11, the image quality was superior to the image formed by corona discharge, and the image was extremely clear. Ta. Example 14 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 202 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, thoroughly washed with water, and dried to clean the surface, was prepared and placed in the deposition chamber 201. It was firmly fixed at a predetermined position of the fixing member 203 located at a predetermined position. In this case, the support 202 is composed of Si and Ge with a purity of 5nine.
Approximately 8.5cm from polycrystalline mixed target 205
I let go. Next, the air in the deposition chamber 201 was evacuated to a degree of vacuum of approximately 1×10 ⁻⁵ Torr. after that,
The heater 204 was ignited to uniformly heat the support to 50° C. and maintain this temperature. After that, the auxiliary valve 224 is fully opened, and the cylinder 209 is
After fully opening the valve 213, the flow rate adjustment valve 2
21 gradually opens and adjusts with the main valve 225, H ₂ gas is supplied from the cylinder 209 to the deposition chamber 2.
The sample was introduced into the deposition chamber 201 so that the degree of vacuum in the chamber 201 was 5.5×10 ⁻⁴ Torr. 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, turn on the high frequency power source 207 and connect the aluminum support 202 and target 2.
A high frequency voltage of 13.56MHz and 1KV is applied between 05 and 05 to cause discharge, and a
- Formation of the semiconductor layer was started and continued for 30 hours. The thickness of the resulting a-semiconductor layer is 20μ
It was hot. 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 cylinder 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 in the deposition chamber 201 reached 100 Torr, the temperature of the heater 204 was raised to bring the temperature of the support to 250° C., 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 was closed, and the valve 226 was opened instead to break the vacuum in the deposition chamber 201 and take it 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 subjected to cascade development and then transferred and fixed onto transfer paper, an extremely clear and high quality image was obtained. Example 15 A-
A semiconductor layer was formed. After that, this sample was deposited in the deposition chamber 2.
01, the removal lid 141 of the apparatus shown in FIG. 1 was removed, and the sample was supported on a rotating roller 144. Next, close the removal lid 141 and main valve 1.
45 to exhaust the air in the heat treatment chamber 131,
The vacuum level is approximately 1×10 ^-5 Torr, and heating furnace 1 is heated.
32 was turned on to raise the temperature inside the heat treatment chamber 131 to 250°C and keep it constant. After that, the valves 134 and 139 are fully opened, and then the flow rate adjustment valve 136 is gradually opened, and O ₃ gas is introduced from the cylinder 133 while adjusting the main valve 145.
The internal pressure of 31 was approximately 100 Torr. When the heat treatment conditions became constant as described above, the sample was moved to the position indicated by the dotted line using the rotating roller 144 and heat treated for 60 minutes. After completing the heat treatment, the electrophotographic image forming member created in this manner is transferred to the rotating roller 14 again.
4, the support body 102 is moved toward the removal lid 141, the valves 145, 134, the flow rate adjustment valve 136, and the valve 139 are closed, and the leak valve 146 is opened instead to break the vacuum in the heat treatment chamber 131 and release the gas to the outside. I took it out. 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. 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 16 The surface of the photoconductive layer formed under the same conditions and procedures as in Example 1 was coated with polyurethane resin.
A surface coating layer having a thickness of μ was formed to obtain an electrophotographic image forming member. Corona discharge was applied to the surface of this electrophotographic image forming member in the dark at a power supply voltage of 6000 V, and then image exposure was performed at an exposure amount of 15 lux·sec to form an electrostatic image. When developed with toner charged by the cascade method and transferred and fixed onto transfer paper, an extremely clear image with high resolution was obtained.

[Brief explanation of the drawing]

FIG. 1 is a schematic explanatory diagram showing an example of an apparatus embodying the present invention, and FIG. 2 is a schematic explanatory diagram showing an example of an apparatus for manufacturing a photoconductive member according to the present invention by a sputtering method. It is a diagram. 101...Deposition chamber, 102...Support, 103
...Fixing member, 105...High frequency power supply, 108-
112...Cylinder, 123-127...Valve,
118-122...Flow rate adjustment valve, 129...
Main valve, 131... Heat treatment chamber, 132...
Heating furnace, 137...High frequency power supply, 138...Inctance coil, 201...Deposition chamber, 202...
...Support, 205...Target, 208-21
1...Cylinder, 216-219...Flow control valve, 225...Main valve.

Claims (1)

[Claims] 1. An amorphous semiconductor layer made of silicon and germanium formed on a support is treated with oxygen,
Amorphous light characterized by heat treatment in an atmosphere containing at least one of nitrogen and an oxygen atom or a compound containing a nitrogen atom, or an activated one thereof. A method for manufacturing a conductive member. 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) Introducing a desired gas into a deposition chamber capable of reducing the pressure to achieve a desired internal pressure, and at least one of the silicon and silicon compounds in the deposition chamber.
generating a gas plasma atmosphere in a space where germanium and at least one of germanium and germanium compounds are present; (b) placed in the deposition chamber in advance and maintained within a temperature range for layer formation; (c) maintaining the gas plasma atmosphere for a sufficient period of time to deposit an amorphous semiconductor layer on the support formed in step (b) above to form an amorphous semiconductor layer to a desired thickness; an amorphous semiconductor layer in an atmosphere containing at least one of oxygen, nitrogen, and a compound containing an oxygen atom or a nitrogen atom, or an activated one thereof. A method for producing an amorphous photoconductive member, comprising the steps of: heat-treating; 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 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.