JPH07181700A - Production of electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To obtain a production method of an electrophotographic photoreceptor by which a uniform and high-quality picture image without image defects or irregular density of the image can be obtd. CONSTITUTION:An electrophotographic photoreceptor is produced by mounting an aluminum base body on a base body holder and forming a functional film of an amorphous material comprising silicon atoms as the source material on the surface of a base body 101 by reduced-pressure vapor phase epitaxy. In this process, the surface of the base body 101 is cleaned with water 132 in which carbon dioxide is dissolved. The source material of the base body holder consists of a material (a) having large thermal conductivity and a material (b) having small coefft. of thermal expansion and small thermal conductivity. The upper or/and lower part of the base body holder is made of the material (b). By this method, production of small image defects is prevented and an electrophotographic characteristics are improved. Further, the electrophotographic photoreceptor which gives uniform and high-quality picture images can be obtd. at low cost.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electrophotographic photosensitive member having a functional film formed on an aluminum substrate.

The present invention particularly relates to a method for manufacturing an electrophotographic photosensitive member in which a non-single crystal deposited film containing silicon atoms and hydrogen atoms is formed as a functional film on an aluminum substrate containing silicon element by a plasma CVD method.

[0003]

2. Description of the Related Art As a substrate for forming a deposited film of an electrophotographic photosensitive member, glass, heat resistant synthetic resin, stainless steel, aluminum, etc. have been proposed. However, in practice, metal is often used in order to withstand electrophotographic processes such as charging, exposure, development, transfer, and cleaning, and to maintain high positional accuracy at all times so as not to deteriorate image quality. Among them, aluminum is one of the most suitable materials as a substrate for an electrophotographic photoreceptor because it has good workability, low cost, and light weight.

A technique relating to the material of the substrate of the electrophotographic photosensitive member is disclosed in JP-A-59-193463 and JP-A-60-2.
No. 62936. JP-A-59-19
No. 3463 discloses that the Fe content of the support is 2000 p.
A technique for obtaining an amorphous silicon electrophotographic photosensitive member with good image quality by using an aluminum alloy having a thickness of pm or less is disclosed. Further, in this publication, after a cylindrical (cylindrical) base body is cut by a lathe and mirror-finished,
A procedure for forming amorphous silicon by glow discharge is disclosed. JP-A-60-262936 discloses that Mg is contained in an amount of 3.0 to 6.0 wt%, and Mn is 0.3 wt% or less and Cr is 0.01 as impurities.
less than 0.1 wt%, Fe less than 0.15 wt%, Si less than 0.1
Disclosed is an extruded aluminum alloy which is suppressed to 2 wt% or less and has excellent vapor deposition property of amorphous silicon consisting of the balance Al. However, these publications do not describe a cleaning method with water containing a specific component.

A technique relating to a method for processing a substrate of an electrophotographic photosensitive member is described in Japanese Patent Laid-Open No. 61-171798. In this publication, a cutting oil according to a specific component is used,
A technique for obtaining an electrophotographic photosensitive member such as amorphous silicon of good quality by cutting a substrate is disclosed.
Further, the publication describes that after cutting, the substrate is washed with triethane (trichloroethane: C ₂ H ₃ Cl ₃ ).

As a technique relating to the surface treatment of the substrate of the electrophotographic photosensitive member, JP-A-58-014841, JP-A-61-273551, and JP-A-63-264764 are known.
Japanese Laid-Open Patent Publication No. 1-130159 and Japanese Laid-Open Patent Publication No. 1-130159 have been proposed.

Japanese Patent Laid-Open No. 58-014841 discloses that after removing a native oxide film on the surface of an aluminum support,
A technique for obtaining a uniform oxide film by immersing in water having a temperature of 60 ° C. or higher is disclosed.

In Japanese Patent Laid-Open No. 61-273551, S
When e and the like are vapor-deposited on an aluminum substrate to prepare an electrophotographic photosensitive member, examples of pretreatment of the substrate include alkali cleaning, trichlene cleaning, ultraviolet irradiation cleaning with a mercury lamp, and before ultraviolet irradiation cleaning. It is described that liquid degreasing cleaning, vapor degreasing cleaning and pure water cleaning are performed as treatments for removing oil and fat adhering to the surface of a cylindrical aluminum substrate.

Japanese Unexamined Patent Publication No. 63-264764 discloses a technique for roughening the surface of a substrate with a water jet.

Japanese Unexamined Patent Publication (Kokai) No. 1-130159 discloses a technique for cleaning an electrophotographic photosensitive member support with a water jet. The publication mentions Se and an organic photoconductor as well as amorphous silicon as an example of the photoconductor, but does not mention any problems peculiar to the plasma CVD method at all.

On the other hand, as a pretreatment method for substrates other than the electrophotographic photoreceptor, Japanese Patent Laid-Open No. 60-876 discloses that ultrapure water is supplied with carbon dioxide gas so as to prevent discharge breakdown due to static electricity on the wafer surface. The technique of blowing is disclosed. But,
This technique is a countermeasure against static electricity generated in a high-resistance substrate such as a wafer, and does not mention a conductive substrate such as aluminum at all.

Various materials such as organic materials such as selenium, cadmium sulfide, zinc oxide, amorphous silicon, and phthalocyanine have been proposed as technologies for element members used in electrophotographic photoreceptors. Among them, non-single-crystal deposited films containing silicon atoms represented by amorphous silicon as a main component, such as hydrogen and / or halogen (eg, fluorine,
Amorphous deposited films such as amorphous silicon that have been compensated with chlorine) have been proposed as high-performance, highly durable, pollution-free photoconductors, some of which have been put to practical use. Japanese Unexamined Patent Publication No. 54-86341 discloses a technique of an electrophotographic photosensitive member in which a photoconductive layer is mainly formed of amorphous silicon.

As a method of forming such a non-single-crystal deposited film containing silicon atoms as a main component, a conventional sputtering method,
Method of decomposing raw material gas by heat (thermal CVD method), method of decomposing raw material gas by light (optical CVD method), method of decomposing raw material gas by plasma (plasma CVD method)
Etc., many methods are known.

The plasma CVD method, that is, the method of decomposing a raw material gas by direct current, high frequency or microwave glow discharge to form a thin film deposited film on a substrate is a method of forming an amorphous silicon deposited film for electrophotography. It is the best choice and is now very practically used. Among them, in recent years, a plasma CVD method using microwave glow discharge decomposition, that is, a microwave plasma CVD method has been industrially attracting attention as a deposited film forming method.

The microwave plasma CVD method has the advantages of a higher deposition rate and higher source gas utilization efficiency than other methods. One example of microwave plasma CVD technology that takes advantage of these advantages is US Pat.
No. 04,518. The technique described in the patent is to obtain a good quality deposited film at a high deposition rate by a microwave plasma CVD method at a low pressure of 0.1 Torr or less.

Further, a technique for improving the utilization efficiency of the raw material gas by the microwave plasma CVD method is disclosed in Japanese Patent Laid-Open No. Sho 60.
No. 186849. The technique described in the publication is generally arranged such that a substrate is arranged so as to surround a means for introducing microwave energy to form an internal chamber (that is, a discharge space) so that the utilization efficiency of raw material gas is greatly enhanced. It is a thing.

Further, Japanese Laid-Open Patent Publication No. 61-283116 discloses an improved microwave technique for manufacturing a semiconductor member. That is, in the publication, an electrode (bias electrode) is provided as a plasma potential control in the discharge space, and a desired voltage (bias voltage) is applied to the bias electrode to control the ion bombardment of the deposited film to deposit the film. Disclosed is a technique for improving the characteristics of the deposited film as it is performed.

When an aluminum alloy cylinder is used as the substrate, these conventional electrophotographic photoreceptor manufacturing methods are specifically carried out as follows.

Lathe with air dieper for precision cutting (PNE
UMO PRECLSION INC. A diamond bite (trade name: Miracle bite, made by Tokyo Diamond) is set in the product) so as to obtain a rake angle of 5 ° with respect to the center angle of the cylinder. Next, while vacuum chucking the substrate to the rotary flange of this lathe, spraying white kerosene from the attached nozzle and suctioning chips from the vacuum nozzle also attached, the peripheral speed was 1000 m / min and the feed speed was 0.
Mirror cutting is performed so that the outer shape becomes 108 mm under the condition of 01 mm / R.

Next, the cut substrate is washed with trichloroethane to remove the cutting oil and cutting chips adhering to the surface.

Next, a deposit mainly composed of amorphous silicon is formed on the mirror-finished and cleaned substrate by the deposition film forming apparatus for the photoconductive member by the glow discharge decomposition method shown in FIG.

FIG. 7 is a schematic sectional view of a typical plasma CVD apparatus. In the figure, (701) shows the entire vacuum reaction vessel, (702) is a cathode electrode which also serves as a side wall of the vacuum reaction vessel, (703) is a gate which is an upper wall of the vacuum reaction vessel, and (704) is a vacuum. It is the bottom wall of the reaction vessel. The cathode electrode (702) is insulated from the top wall (703) and the bottom wall (704) by an insulator (705).

Reference numeral (706) denotes a substrate which is mounted in a metal substrate holder (707) made of a single material such as aluminum and placed in a vacuum reaction vessel. The substrate (706)
Is grounded to serve as an anode electrode. Substrate (7
06) is provided with a heater for heating the substrate (708) for heating the substrate to a predetermined temperature before film formation,
It is used to maintain the substrate at a predetermined temperature during film formation or to anneal the substrate after film formation. (70
Reference numeral 9) is a deposition gas forming source gas introduction pipe, which is a gas release hole (71) for releasing the source gas into the vacuum reaction space.
0) are provided in large numbers, and the source gas introduction pipe (70
The other end of 9) communicates with the deposited film forming raw material gas supply system (712) through a valve (711). (713)
Is an exhaust pipe for evacuating the inside of the vacuum reaction container, and a vacuum exhaust device (71) is provided via an exhaust valve (714).
It communicates with 5). (716) is the cathode electrode (7
02) is a voltage application means.

The method of operating the deposited film forming apparatus by the plasma CVD method is performed as follows. That is,
The gas in the vacuum reaction container is evacuated through the exhaust pipe (713), and the heating heater (708) heats and holds the substrate (706) at a predetermined temperature. Next, for example, in the case of forming an a-SiH deposited film through the raw material gas introduction pipe (709), a raw material gas such as silane is introduced into the vacuum reaction vessel, and the raw material gas is supplied through the raw gas introduction pipe (709). The raw material gas is released into the vacuum reaction vessel through the hole (710).
Simultaneously with this, a high frequency, for example, is applied between the cathode electrode (702) and the substrate (anode electrode) (706) from the voltage applying means (716) to generate plasma discharge. Thus, the raw material gas in the vacuum reaction vessel is excited and excited to generate seeds, and radical particles such as Si ^* , SiH ^*, etc. ( ^* represents an excited state), electrons, ion particles, etc. are generated, and these particles or between these particles or A chemical interaction between these particles and the surface of the substrate forms a deposited film on the surface of the substrate.

When forming such an electrophotographic photosensitive member made of, for example, a-Si, it is necessary to transport and hold the cylindrical substrate in the vacuum reaction container. Therefore, the substrate holder is inserted into the cylindrical substrate. Is done. Further, as disclosed in, for example, Japanese Patent Application Laid-Open No. 60-86276, it is necessary to provide auxiliary bases above and below the base for the purpose of making the characteristics uniform. It is common practice to insert a substrate holder into the.

[0026]

However, in these conventional methods for producing an electrophotographic photosensitive member, the requirements for optical and electrical characteristics with a uniform film quality are satisfied, and the image quality is high during image formation by the electrophotographic process. There remains a problem to be solved that it is difficult to obtain a deposited film constantly and stably with a high yield (high yield).

That is, at present, the electrophotographic apparatus has higher image quality,
High speed and high durability are desired. As a result, in the electrophotographic photoreceptor, it is required to further improve the optical characteristics and electrical characteristics and improve the uniformity, and at the same time, to extend the durability in all environments while maintaining high charging ability and high sensitivity. ing. Further, in recent years, in order to improve the image characteristics of the electrophotographic apparatus, the optical exposure system, the developing apparatus, the transfer apparatus, etc. in the electrophotographic apparatus have been improved. As a result, the image characteristics of the electrophotographic photosensitive member are improved more than ever before. Came to be demanded.

As a result, the problem that the characteristic of the electrophotographic photosensitive member varies locally is not always a pain in a conventional copying system of speed and resolution, and can be ignored in some cases, but lasers and the like can be ignored. This is a major problem in high-speed continuous image forming systems such as high-speed copying systems, facsimile systems, printer systems, etc. that use the coherent light source of Since it becomes obvious, it has become a big problem.

Further, as a result of improving the resolution of the image, it is commonly called "poti". There has been a demand for reduction of white-spotted or black-spotted image defects, in particular, reduction of minute spots, which has not been a serious problem in the past. In particular, with regard to "potty", most of the causes are abnormal growth of a film called a spherical projection, and it is very important to reduce the number of occurrences.

Further, the conventional copying application has been mainly for originals of only printed characters (so-called line copy), but as the image quality of the copying machine has recently increased, many originals including halftones such as photographs are copied. And
These problems are serious and are what are required to be solved.

Therefore, while the characteristics of the electrophotographic photoreceptor itself are improved, improvements are made from a comprehensive point of view such as the layer structure, the chemical composition of each layer and the manufacturing method so that the above problems can be solved. Is required. An object of the present invention is to provide an easy-to-use method for manufacturing an electrophotographic photosensitive member which overcomes various problems in the conventional method for manufacturing an electrophotographic photosensitive member as described above and which can be stably formed at low cost with high yield. Especially.

Another object of the present invention is plasma CV.
It is an object of the present invention to provide a method for producing an electrophotographic photosensitive member which can solve the problem of occurrence of particularly noticeable image defects in the method D and can obtain a uniform high-quality image.

[0033]

The present invention is intended to solve the above-mentioned problems, and the gist thereof is to mount an aluminum base on a base holder and deposit silicon atoms on the surface of the base by a reduced pressure vapor deposition method. In the method for producing an electrophotographic photosensitive member which forms a functional film made of an amorphous material as a base material, the base body is washed with water in which carbon dioxide is dissolved, and the base material of the base body holder is (A) a material having a large thermal conductivity, and (b) a material having a small thermal expansion coefficient and a small thermal conductivity, at least a portion facing the base is made of the material (a), and the upper part of the base holder or In the method of manufacturing an electrophotographic photosensitive member, the / and the lower part are composed of the material of (b).

Here, the conductivity of the water in which the carbon dioxide is dissolved may be 2 μS / cm or more and 40 μS / cm or less.

The pH of the water in which the carbon dioxide is dissolved
May be 3.8 or more and 6.0 or less.

The water in which carbon dioxide is dissolved may be water in which carbon dioxide is dissolved in pure water having a resistivity of 1 MΩ · cm or more.

The aluminum base may be an aluminum base containing at least a small amount of silicon atoms.

The aluminum base may be an aluminum base containing at least 1 ppm to 1 wt% of silicon atoms.

The thermal conductivity of (a) above is 200 (W
/ M · K) or more and the thermal conductivity of (b) above is 50
(W / m · K) or less, thermal expansion coefficient of 20 (10 ^-6 K ^-1 )
It may be the following.

The materials (a) and (b) may be metallic materials.

In addition, the surface of the portion of the substrate made of the material (a) on the substrate side has a ten-point average roughness of 10 μm to 70 μm
It may be the following.

Further, the distance between the base made of the material (a) and the substrate may be 3 mm or less.

In addition, after heating the substrate in a vacuum container dedicated to heating, the substrate is moved to a reaction container in a vacuum, and a light-receiving layer made of an amorphous material containing silicon atoms as a base material is formed on the surface of the substrate. A deposited film forming apparatus that does this may be used.

In the reduced pressure vapor deposition method, a cylindrical substrate mounted on a substrate holder is arranged so as to surround a discharge space in a reaction vessel that can be substantially sealed, and a microwave introducing means is provided. A microwave discharge plasma containing a reactant derived from the source gas and contributing to film formation is formed, and a bias voltage is applied to an electrode provided in the discharge space so that the surface of the substrate is in the discharge space and in the non-discharge space. Alternatively, a method may be used in which the photoreceptive layer made of an amorphous material having silicon atoms as a base material is formed on the surface of the base while moving the base so as to alternately pass through.

[0045]

The method for producing an electrophotographic photosensitive member of the present invention uses a substrate whose surface is washed with water in which carbon dioxide is dissolved,
The base material is (a) a material having high thermal conductivity, and
(B) A substrate made of a material having a small coefficient of thermal expansion and thermal conductivity, at least a portion facing the substrate is made of the material of (a), and an upper portion and / or a lower portion is made of the material of (b). By mounting it on a holder and forming a deposited film made of an amorphous material containing silicon atoms as a base material on the surface of the substrate by a reduced pressure vapor deposition method, the spatial variation in the characteristics of the deposited film is reduced, Image density unevenness can be greatly reduced.

The inventors of the present invention have made earnest studies on the reduction of the image density unevenness, and have found that the image density unevenness is correlated with the discoloration of the inner surface of the substrate after the deposited film is formed. That is, there is a difference in image density depending on the portion where the surface of the inner surface of the substrate is not discolored, the portion where the surface is discolored, and the degree of discoloration. The degree of discoloration on the inner surface of the substrate is non-uniform within the surface, and the place of occurrence and the degree of discoloration differ for each deposited film formation (for each lot).

The inventors of the present invention consider the mechanism by which the image density unevenness occurs due to the discoloration of the inner surface of the substrate as follows.

When, for example, an amorphous silicon deposited film is formed on a substrate by the plasma CVD method, the reaction is the decomposition process of the source gas in the vapor phase, the transport process of active species from the discharge space to the substrate surface, and the substrate surface. Surface reaction process 3
You can think separately. Above all, the surface reaction process plays a very important role in determining the structure of the completed deposited film. These surface reactions are greatly affected by the temperature, material, shape, adsorbed substance, etc. of the surface of the substrate. The growth process on this substrate will be described in more detail below by taking amorphous silicon containing hydrogen as an example. The decomposed species that have been decomposed and transported in the plasma adhere to the substrate to form a network of the amorphous silicon film. However, in the growth surface of amorphous silicon where the network is not completed three-dimensionally, desorption of hydrogen atoms is performed. Chemical reactions (relaxation process) in the direction of energy stability due to few structural defects due to separation, bonding of hydrogen atoms and silicon atoms to dangling bonds, rearrangement of atoms with high energy bond, etc. Occur. As a result, as a deposited film, dangling bonds are reduced, gap level density is reduced, and Si--H ₂ bonds are reduced to reduce Si.
A decrease, such as predominantly -H bonds, is observed. Since these reactions are controlled by the thermal energy of the substrate, if the substrate temperature varies locally, it is directly affected by the characteristics of the deposited film, and as a result, the mobility of the charges (photocarriers) is locally affected. Inhomogeneity may occur, or the composition and structure of the interface between the deposited film and the substrate may change, resulting in localized nonuniformity of the charge injection property from the substrate during the steps of the electrophotographic process. As a result, a difference in surface potential sufficient to change the image density appears, resulting in uneven image density on the obtained image.

As described above, when the light receiving member made of a-Si is formed by the vapor phase growth method such as the plasma CVD method, it is necessary to satisfy the uniformization and stabilization of the substrate temperature at the same time. This is particularly important when forming a relatively thick deposited film such as a light receiving member for electrophotography.

As a method for heating the substrate, there is a means for directly heating the vapor phase growth surface by using infrared rays or the like, but it is usually difficult to provide a heating means on the vapor phase growth side in terms of mounting. A heating means is provided inside the holder.

Therefore, in order to heat the substrate to a predetermined temperature, the heat received by the inner surface of the substrate holder is indirectly transmitted to the substrate. And, especially in continuous manufacturing,
The base member consisting of the base and the base holder needs to be docked with the heating means which is the fixing member through the carrying step, and further, because the base member is rotated to make the characteristics uniform, It is desirable that the base member and the heating means are not in contact with each other. In that case, the heat is transferred mainly by the heat radiation from the heating means to the inner surface of the substrate holder, and finally by the heat radiation from the substrate holder to the inner surface of the substrate. Therefore, when color unevenness occurs on the inner surface of the substrate, the thermal emissivity changes depending on the color, so that it is considered that temperature unevenness occurs on the substrate surface corresponding to the color unevenness and image density unevenness occurs.

According to the present invention, the discoloration of the inner surface of the substrate can be significantly suppressed, and the discoloration unevenness can be eliminated, whereby the image density unevenness can be greatly improved. Although the mechanism has not been clarified yet, the present inventors currently think as follows.

The discoloration of the inner surface is reduced by lowering the temperature of the substrate and becomes more prominent by raising the temperature of the substrate, and is therefore induced by the temperature. Therefore, it is considered that the substance existing on the surface of the inner surface is deteriorated by the temperature rise, and the result appears as the discoloration of the inner surface. In addition, it is considered that the uneven discoloration in the surface is caused by the non-uniformity of the substance existing on the surface of the inner surface or the non-uniformity of the heating method.

According to the present invention, since carbon dioxide is dissolved in water, carbonate ions are present in water. This carbonate ion causes some alteration of the substance existing on the surface of the inner surface of the substrate. In this case, the deterioration due to the carbonate ion has a different mechanism from the deterioration due to the temperature rise, so that the inner surface of the substrate is not discolored at all. Further, in the substance thus modified by the carbonate ion, discoloration is significantly reduced even when the temperature is raised.

Further, it is preferable to use a substrate holder in which a portion facing the substrate is made of a material having a large thermal conductivity, and an upper portion and / or a lower portion of the substrate holder is made of a material having a small thermal expansion coefficient and a small thermal conductivity. As a result, it is possible to uniformly heat the inner surface of the substrate, and it is possible to eliminate unevenness in the surface of discoloration and unevenness for each lot.

The heating of the substrate is carried out by first setting the substrate on a substrate holder, then installing the substrate holder on, for example, a stand in a vacuum container or a rotating mechanism for rotating the substrate member, and heating the substrate by heating means. The substrate surface is heated to a predetermined temperature.

As a method for heating the substrate, there is a means for directly heating the vapor phase growth surface using infrared rays or the like, but it is usually difficult to provide a heating means on the vapor phase growth side in terms of mounting. A heating means is provided inside the holder.

Therefore, in order to heat the substrate to a predetermined temperature, the heat received by the inner surface of the substrate holder is indirectly transmitted to the substrate. And, especially in continuous manufacturing,
The base member consisting of the base and the base holder needs to be docked with the heating means, which is the fixing member, through the carrying process, and further, because the base member is rotated, the base member and the heating means are not in contact with each other. It is desirable to put it in a state. In that case, the heat transfer is mainly performed by heat radiation from the heating means to the inner surface of the substrate holder. The received radiant heat is transmitted through the inside of the substrate holder by heat transfer, and is further transmitted to the substrate mounted on the surface of the substrate holder. Since the base body is in close contact with the base body holder, the base body temperature is directly influenced mainly by the temperature distribution of the base body holder. Further, in the case of the plasma CVD method, in order to improve the quality of the deposited film, there is a case where the internal pressure during formation of the deposited film is set to the low pressure side. This is because the raw material gas is sufficiently decomposed to prevent energy loss due to the polymerization reaction in the gas phase of the active species whose activity has been increased, which promotes the surface reaction of the substrate surface and is activated. This is because hydrogen is allowed to reach the surface of the substrate without a gas phase reaction and the relaxation process is further promoted. However, when considering the relationship between pressure and substrate temperature,
The lower the pressure, the more susceptible it is to the substrate holder. This is because at low pressure, the heat transfer from the substrate is mainly due to heat conduction from the substrate holder (or heat conduction to the substrate holder) that is in close contact with the substrate rather than radiation from the space (or radiation to the space). It is because

As in the present invention, the portion of the substrate holder facing the substrate is made of a material having a large thermal conductivity, and the upper portion and / or the lower portion of the substrate holder is made of a material having a small coefficient of thermal expansion and thermal conductivity. By doing so, for example, when the positional relationship between the substrate holder and the heating means is deviated, or when the deposited film is formed, the temperature (internal pressure, gas type, etc.) changes unevenly and the temperature becomes uneven. Even in such a case, since the heat transfer of the base holder facing the base is good, it is possible to prevent the heat from rapidly moving in the base holder and causing a temperature difference in the base holder itself. However, the above-mentioned action cannot be obtained in a conventional substrate holder made of a single material such as aluminum, and at the same time, as in the present invention, the upper and / or lower portion of the substrate holder is made of a material having a small coefficient of thermal expansion and thermal conductivity. Must consist of As shown in FIGS. 2A and 2B, the substrate holder is in contact with, for example, the rotating shaft, the pedestal, or the ground surface. These contact portions will typically be the top and / or bottom of the substrate holder. Regarding the escape of heat from the substrate holder, the heat conduction from the contact portion is mainly due to the radiation to the space as described above. Therefore, in a material having high heat conduction such as aluminum, a large amount of heat escapes from the contact portion, rather the temperature uniformity in the substrate holder is disturbed, and thus the substrate temperature uniformity is impaired.

As described above, the substrate washed with water in which carbon dioxide is dissolved and the portion facing the substrate are made of a material having a large thermal conductivity, and the upper portion and / or the lower portion of the substrate holder have a coefficient of thermal expansion and By simultaneously using the substrate holder composed of a material having a small thermal conductivity, the synergistic effect of the substrate holder improves the uniformity of the deposited film and the image density unevenness in halftone is greatly improved.

Further, since the discharge is made uniform and stabilized during the formation of the deposited film according to the present invention, the unevenness of the image density is further improved, and the film quality of the deposited film is improved by the above-mentioned uniformization of the substrate temperature and the synergistic effect. Can be improved.

As described above, when considering the growth mechanism of the deposited film by the plasma CVD method, the discharge state is closely related to the decomposition process of the source gas and the transportation process of the decomposed species to the substrate.

If the discharge state is unstable during the formation of the deposited film, the types and amounts of radical particles, electrons, ion particles, etc. generated in the plasma described above, and the energies of these active species will change. . Therefore, the relaxation process of the deposited film also changes, which affects the quality of the deposited film. Therefore, particularly in the case of forming a relatively thick deposited film such as a light receiving member for electrophotography, it is necessary to achieve uniformization and stabilization of the substrate temperature and the discharge state at the same time.

Regarding the stability of the discharge, the parameters that influence the discharge state include the flow rate of the raw material gas, the discharge power, the internal pressure, and the like. These are generally the flow rate of the raw material gas, for example, in the case of a mass flow controller or the internal pressure, a vacuum gauge. And so on. On the other hand, one of the parameters that influence the discharge state is the dimension of the discharge space. Particularly, in the device as shown in FIG. 7, the distance between the electrodes (distance between the substrate and the cathode electrode)
Is a parameter that greatly affects the discharge state. The distance between the electrodes depends on the installation state of the substrate holder. However, the installation state of the substrate holder is affected by the heating process. For example, in the case of a conventional substrate holder made of a single aluminum material, when the substrate surface temperature is heated to 200 to 400 ° C., the substrate holder itself (depending on the shape and the length) undergoes thermal expansion of several mm or more. . Therefore, even if it is installed accurately at room temperature, a positional deviation or inclination occurs at the contact portion such as the rotating shaft or the stand when the heating is completed. Particularly in the case of the electrophotographic light-receiving member, since it has a certain length in the generatrix direction (vertical direction), even a slight positional deviation at the contact portion causes a large deviation at the other end. As a result, the discharge state becomes uneven in the vertical direction or the circumferential direction.

In the present invention, since the deposited film is formed by using the substrate holder whose upper portion and / or lower portion (contact portion with the rotating shaft etc.) is made of a material having small heat conduction and thermal expansion, the above-mentioned positional deviation and The inclination can be reduced, and as a result, the discharge state can be stabilized.

As described above, in the method of forming a light-receiving member in which the light-receiving layer made of an amorphous material having silicon atoms as a base material is formed on the surface of the substrate by the reduced pressure vapor phase growth method, as in the present invention, The deposited film forming method is very effective. That is, 1) it is effective for the uniformity of the substrate temperature, and 2) it is effective for the stability of the discharge state, and by achieving the above effects at the same time, there are variations in the characteristics of the light-receiving layer, or in the characteristics of each manufacturing lot. The variation of can be extremely reduced. Further, the combined effect of 1) and 2) improves the film quality of the light-receiving member, and in particular, the charging property can be improved.

Further, such an effect is obtained by arranging a cylindrical substrate mounted on a substrate holder so as to surround a discharge space in a reaction vessel which can be substantially sealed as shown in FIG. A microwave introduction means is provided to form a microwave discharge plasma containing a reactant derived from a raw material gas and contributing to film formation, and an electrode bias voltage provided in the discharge space is applied to bring the surface of the substrate into the discharge space. Particularly in the method of forming the light receiving member, the light receiving layer is formed on the surface of the base while moving the base so as to alternately pass through the interior and the non-discharge space It is effective.

Microwave plasma CV having the above configuration
In the D method, the dimension of the discharge space is completely determined by the positional relationship of the substrate. Therefore, for example, if a positional deviation occurs when the substrate is installed, the positional deviation directly affects the discharge state. Further, since the base body rotates, the positional deviation is increased due to the rotation, and so-called rotational shake (eccentricity) occurs, so that the discharge state is largely changed and fluctuated. Further, as the discharge state changes, the type and amount of ions generated in the discharge space and the energy possessed by the ions also change, resulting in variations in ion bombardment to the deposited film and uneven film quality of the deposited film. turn into. In some cases, the quality of the deposited film is significantly deteriorated.

Further, the deposited film forming surface inevitably alternately passes through the discharge space where plasma is generated and the non-discharge space where plasma is not generated. The microwave plasma CVD method has a much higher plasma temperature than the high frequency plasma CVD method. Therefore, immediately after the formation of the deposited film (immediately after turning from the non-discharge space to the discharge space), the deposited film formation surface continues to obtain thermal energy from the plasma, and immediately after the end of formation of the deposited film (immediately after turning from the discharge space to the non-discharge space). ), On the contrary, will release thermal energy. As a result, the temperature at the time of forming the deposited film differs between the deposited film formed immediately after the formation of the deposited film and the deposited film formed immediately after the formation of the deposited film (immediately after facing the discharge space to the non-discharge space). I will end up. In the case of the microwave plasma CVD method, the internal pressure during formation of the deposited film is lower than that of the high frequency plasma CVD method (0.1 Torr or less). The heat transfer from the substrate at such a low pressure is further mainly conducted by heat conduction to the substrate holder, which is in close contact with the substrate, rather than radiation to the space. Therefore, as described above, the transfer of heat at the contact portion with the rotating shaft or the like becomes more remarkable.

In this way, the discharge space is surrounded,
Arrange the cylindrical substrate mounted on the substrate holder, use microwave discharge plasma and external electric bias voltage together,
A light-receiving member that forms a light-receiving layer made of an amorphous material having silicon atoms as a base material on the surface of a substrate while moving the substrate so as to alternately pass through a discharge space and a non-discharge space on the surface of the substrate. In the forming method of (1), the substrate temperature and the discharge state become more important than those of the apparatus of other configurations, so that the forming method of the present invention is particularly effective.

Further, according to the present invention, the number of spherical projections generated can be reduced, and as a result, white spot-like or black spot-like image defects commonly called "potches" can be greatly reduced.

According to the studies made by the present inventors, the cause of the image defect that occurs when the aluminum substrate is used is (A) dust or the like adheres to the substrate and becomes a nucleus. (B) Surface defects of the substrate serve as nuclei. Can be roughly divided into (A) The adhesion of dust etc. is due to cleaning the place where the substrate is handled, such as cutting and washing, and strict cleaning of the inside of the film forming furnace, and cleaning of the substrate surface immediately before the formation of the deposited film. It was possible to prevent it. Conventionally, this object has been achieved by washing with a chlorine-based solvent such as trichloroethane. However, in recent years, the use of such chlorine-based solvents has come to be restricted due to the destruction of the ozone layer and the like, so that it is necessary to newly examine this problem. Also, as mentioned above,
Image defects need to be further reduced.

On the other hand, it was very difficult to reduce the defects of (B) as compared with the conventional method.

According to the study of the present inventor, there is a locally high hardness portion in aluminum, and as a preprocessing prior to the formation of a deposited film, the high hardness of the high hardness is applied to the blade of the processing machine at the time of surface processing such as cutting. It was revealed that the cause of (B) was that the part was scooped out and a surface defect was formed on the aluminum substrate.

Further, in order to prevent these phenomena, it is usually preferable that the amount of impurities contained in aluminum is small, but very high-purity aluminum is used during melting for processing the raw material aluminum into the shape of the substrate. Inevitably, the generated oxide grows, which causes the aforementioned defects. It has been revealed that it is effective to contain a silicon atom in order to prevent this.

When the surface of the substrate is machined and then washed with a chlorine-based solvent such as trichloroethane, image defects due to the surface properties of the substrate can be sufficiently prevented by the above procedure.

However, in recent years, these chlorine-based solvents cannot be easily used due to further environmental problems, and therefore the present inventor also studied cleaning. As a result, it was found that aluminum is corroded by water, and particularly when aluminum containing these silicon atoms is corroded by water during cleaning, the corrosion by water becomes remarkable mainly in the part where the number of silicon atoms is locally large. did.

This phenomenon was more remarkable as the temperature of water was higher, and was more remarkable when magnesium was included in aluminum together with silicon atoms for the purpose of improving machinability. Various corrosion inhibitors have been proposed in order to prevent corrosion of aluminum, but when an aluminum substrate containing silicon is used as a substrate of an electrophotographic photoreceptor as in the present invention, a small amount of it may be present on a substrate having a large area. However, the effect is insufficient because the defects generated in 1) cause a problem, and further, these corrosion inhibitors remain on the surface of the substrate in a trace amount after cleaning, which adversely affects the electrophotographic characteristics after forming the deposited film. That is, when a component other than a component that is rapidly volatilized simultaneously with water is attached to the surface of the aluminum substrate, adverse effects such as stains on an image occur when an electrophotographic photosensitive member is produced, and therefore, the conventional corrosion inhibitor Its use is limited.

The present inventors have pointed out that the generation of the above defects can be suppressed by performing some treatment on the water used for the cleaning for removing the adhesion of dust before forming the deposited film. As a result of intensive research, the present invention has been completed.

Although the mechanism of the present invention has not been clarified in many points, the present inventor now thinks as follows.

A portion of the aluminum surface, which is partially exposed and has a large amount of silicon atoms, forms a local battery with the surrounding ordinary aluminum portion to promote corrosion.

On the other hand, carbon dioxide dissolved in water becomes carbonate ions in water, and is attracted to these local battery parts to cover the surroundings, thereby preventing oxygen and the like in the water from approaching and effectively preventing corrosion. Further, the carbonate ions cause some alteration on the surface of the portion containing many silicon atoms, thereby preventing abnormal growth from occurring in the portion where the deposited film is formed.

Furthermore, the method for producing an electrophotographic photosensitive member of the present invention has the effect of reducing the number of spherical projections generated, and as a result, reducing white dot-like or black dot-like image defects commonly called "potches". was gotten.

The cause of this result is inferred as follows, although it is not clear.

With respect to the spherical protrusions, it has been confirmed that dusts adhering to the surface of the substrate cause dusts to start the growth of the deposited film.

Therefore, the substrate before film formation is precisely cleaned, mounted on a substrate holder in a dust-controlled environment such as a clean room, and transported in a vacuum reaction container to prevent dust from adhering to the substrate as much as possible. I tried to avoid it. Although the substrate is carried into the vacuum reaction container in a clean state as described above, there is a cause of dust adhesion even in the vacuum reaction container. One of them is the adhesion of dust from the basic holder.

In a normal environment, dust generation from the substrate holder is not a serious problem, but dust generation becomes a problem in the step of heating the substrate for forming the light receiving member.

That is, the substrate holder undergoes thermal expansion when the substrate is heated. At this time, the dust adhering to the inside of the substrate holder is released due to the shape change of the surface and stays or accumulates in the vacuum container. Therefore, the inside of the vacuum reaction vessel is contaminated with dust, and the dust adheres to the substrate surface,
Spherical protrusions will occur. In particular, since the upper part and / or the lower part of the base holder comes into contact with the rotating shaft or the like as described above, it is considered that the amount of dust existing on the surface of the support holder or generated from the surface is larger than that of other parts.

According to the forming method of the present invention, the upper portion or /
It is considered that since the support holder made of a material having a small coefficient of thermal expansion is used for the lower part and the lower part, the desorption of dust due to the change in surface shape due to the above-mentioned thermal expansion is reduced.

Further, such an effect is particularly effective in a light-receiving member forming apparatus provided with a dedicated vacuum container for each process as shown in FIG. 6, for example.

The apparatus of FIG. 6 will be described. FIG. 6 is a layout view of the entire deposited film forming apparatus, and (601) is a vacuum charging container for mounting a substrate on a substrate holder in a clean atmosphere to create a vacuum. . (602) is a vacuum heating container for heating and holding the substrate at a predetermined temperature, (603) is a vacuum reaction container for forming the deposited film, (604) is cooling the substrate etc. after the deposited film is formed, It is a vacuum cooling container for taking out. In (605), the substrate holder is attached to each processing container (60
1), (602), (603), (604) is a vacuum transfer container for moving to each value.

(611), (612), (613),
(614) is an exhaust device for evacuating each processing container,
In (621), (622), (623) and (624), the vacuum transfer container (605) is the vacuum processing container (601),
When connected to (602), (603) and (604), the gate valve (635) and the gate valve (631),
An exhaust device for evacuating the spaces (632), (633), and (634). That is, for example, when the substrate holder is taken in and out of the vacuum reaction container (603), the gate valve (635) of the vacuum transfer container (605) is brought into close contact with the gate valve (632) of the vacuum heating container (602), and the gate valve ( The space between 635) and the gate valve (632) is evacuated by the exhaust device (622). Next, the gate valves (632) and (622) are opened, and the heated substrate holder is carried out from the vacuum heating container (602) by the vertical movement mechanism (not shown) provided in the vacuum transfer container (605). In the same operation, the vacuum reaction vessel (60
3) Bring the substrate holder into the inside.

After that, the vacuum reaction vessel (6
In 03), a deposited film is formed on the substrate.

Finally, the substrate holder is carried into the vacuum cooling container (604), and after cooling the substrate in the vacuum cooling container (604), the inside of the vacuum cooling container (604) is brought to atmospheric pressure and the substrate is taken out.

The reason why it is particularly effective in the apparatus for forming a light-receiving member provided with a dedicated vacuum container for each such treatment is that the substrate holder and the like heated in the vacuum heating container (602) are as described above. Dust is easily generated.
It is considered that since the base body and the base body holder are moved under such a situation, they are easily affected by dust generation from the base body holder.

Further, according to the forming method of the present invention, the durability can be remarkably improved while maintaining excellent electric characteristics and image characteristics.

That is, since the spherical projections are reduced as described above, even if a large amount of images are continuously formed, the cleaning blade and the separating claw are less damaged, and the cleaning property and the transfer paper separating property are improved. . Therefore, the durability of the image forming apparatus can be dramatically improved. Furthermore, since the number of spherical protrusions is reduced, the loss of spherical protrusions caused by the sliding contact between the transfer paper and the cleaning blade and the light receiving member is greatly reduced, reducing the increase in “pots” due to long-term use. can do.

Further, as an unexpected effect of the present invention, improvement in electrophotographic characteristics was observed.

This is because the carbonate ions increase the activity of the surface by uniformly and slightly dissolving the entire aluminum surface, and can form an interface capable of exchanging charges favorably when forming a deposited film. Therefore, it is considered possible to improve the electrophotographic characteristics such as improvement of charging and reduction of residual potential.

Further, in the present invention, the pre-washing step is provided after the cutting step and before the washing step of water in which carbon dioxide is dissolved, so that the oils and fats and the halogen-based residue which hinder the effect of the present invention are completely removed. This enhances the above-mentioned effect. In particular, the pre-cleaning step makes it possible to maximize the effect of the present invention by performing ultrasonic cleaning in water or water containing a surfactant.

The present invention will be described in more detail below.

An example of the procedure for actually forming an electrophotographic photosensitive member by the electrophotographic photosensitive member manufacturing method of the present invention using an aluminum alloy cylinder as a base is shown in FIG. A typical example of a base member for explaining the manufacturing method of the present invention is shown below, and the deposited film forming apparatus shown in FIGS.

Lathe with air damper for precision cutting (PNE
UMO PRECLSION INC. A diamond bite (trade name: Miracle bite, made by Tokyo Diamond) is set in the product) so as to obtain a rake angle of 5 ° with respect to the center angle of the cylinder. Next, while vacuum chucking the substrate to the rotary flange of this lathe, spraying white kerosene from the attached nozzle, and suctioning cutting chips from the vacuum nozzle also attached, the peripheral speed was 1000 m / min and the feed rate was 0.01 mm. Under the condition of / R, mirror cutting is performed so that the outer shape becomes 108 mm.

With respect to the substrate after cutting, the substrate surface is treated by the substrate pretreatment device. The substrate pretreatment apparatus shown in FIG. 1 comprises a processing section (102) and a substrate transfer mechanism (103). The processing section (102) is provided with a substrate loading table (11
1), a substrate pre-cleaning tank (121), a cleaning tank (131) with carbon dioxide-dissolved water, a drying tank (141), and a substrate unloading table (151). Pre-cleaning tank (121),
Both the cleaning tank (131) with water in which carbon dioxide is dissolved are equipped with a temperature control device (not shown) for keeping the temperature of the liquid constant. The transport mechanism (103) includes a transport rail (16
5) and the transfer arm (161), the transfer arm (1
61 is a moving mechanism (1) that moves on the rail (165).
62), a chucking mechanism (163) for holding the base body (101), and an air cylinder (164) for moving the chucking mechanism (163) up and down.

After cutting, the substrate (101) placed on the input table (111) is washed by the transfer mechanism (103) into the cleaning tank (12).
It is transported to 1). The cutting oil and chips adhering to the surface are cleaned by ultrasonic treatment in the surfactant aqueous solution (122) in the pre-cleaning tank (121).

Next, the substrate (101) is provided with a transfer mechanism (10
3) Washing tank with water in which carbon dioxide is dissolved (13)
It is transported to 1) and kept at a temperature of 25 ° C. and further washed with water in which carbon dioxide is dissolved. The conductivity of carbon dioxide-dissolved water is approximately 10 μS / by measuring the conductivity at any time with an industrial conductivity meter (trade name: α900R / C, manufactured by Horiba Ltd.), and dissolving carbon dioxide if necessary.
Controlled to maintain cm. The substrate (101) that has been washed with water in which carbon dioxide is dissolved is moved to the drying tank (141) by the transport mechanism (103), and is dried by blowing high-temperature high-pressure air from the nozzle (142).

The substrate (101) after the drying step is carried to the carry-out table (151) by the carrying mechanism (103).

Next, the substrate after the cutting and pretreatment is mounted on the substrate holder as shown in FIGS. 2A and 2B, and the plasma CVD shown in FIGS.
A deposition film mainly composed of amorphous silicon is formed by a deposition film forming apparatus by the method.

In FIGS. 2A and 2B, (200)
Is a substrate holder, and the substrate holder (200) is
A part composed of a material with high thermal conductivity (200
(A)) and a portion (200 (b)) made of a material having a small coefficient of thermal expansion and thermal conductivity. (200 (a))
Are located so as to face the base body (201).
(200 (b)) is the base holder (2
00) and contacts the rotating shaft (205) on the inner surface, and also forms a carrying handle portion (206). In FIG. 2 (B), the substrate holder (200) is located at the upper and lower portions, the lower portion is in contact with the stand (207), and the upper portion also forms a handle portion (206) for transportation.

The substrate holder (200) has a heating means (2
Radiant heat from 04) is directly received on the inner surface. The heat received on the inner surface is transferred to the substrate holder (200), especially (200
(A)) It is transmitted by heat conduction inside, and further transmitted to the base body (201) adhered to the surface of the base body holder (200).

FIG. 2 shows a typical constitutional example, and the auxiliary base portion (203) shown may be omitted if necessary.

The apparatus and method for forming the deposited film by the high frequency plasma CVD method and the microwave plasma CVD method will be described in detail below.

FIG. 3 shows a high frequency plasma CVD method (hereinafter referred to as "R
It is a schematic block diagram which shows an example of the manufacturing apparatus of the electrophotographic photosensitive member by the method (it describes with F-PCVD).

The structure of the deposited film manufacturing apparatus by the RF-PCVD method shown in FIG. 3 is as follows. This apparatus is roughly classified into a deposition apparatus (300) and a source gas supply apparatus (3
30), and an exhaust device (not shown) for reducing the pressure inside the reaction container (301). Deposition device (30
In the reaction vessel (301) in (0), a substrate made of a material having a large thermal conductivity (303 (a)) and a material having a small thermal expansion coefficient and a small thermal conductivity (303 (b)). A conductive cylindrical substrate (302) mounted on a holder (303), a substrate heating heater (304), a source gas introduction pipe (305) are installed, and a high frequency matching box (306) is further connected.

The source gas supply device (330) is made of SiH.
_{4, H 2, CH 4,} NO, B 2 H 6, GeH 4 , etc. raw material gas cylinder (331-336) and valves (341-3
46, 351-356, 361-366) and a mass flow controller (371-376),
The cylinder of each source gas is connected to the gas introduction pipe (305) in the reaction container (301) via the valve (380).

The deposited film can be formed using this apparatus, for example, as follows.

First, the reaction vessel (301) is made of a material having a high thermal conductivity (303 (a)) and a material having a low thermal expansion coefficient and a low thermal conductivity (303 (b)). The cylindrical substrate (302) attached to (303) is installed, and the inside of the reaction container (301) is evacuated by an exhaust device (not shown) (for example, a vacuum pump).

Then, the heater for heating the substrate (304) is turned on. Then, the inner surface of the substrate holder (302) directly receives the radiant heat from the substrate heating heater (304). The heat received on the inner surface is transferred by heat conduction mainly inside (303 (a)) of the base body holder (303), and further, of the cylindrical base body (302) adhered to the surface of the base body holder (303). The temperature is transmitted to the inner surface and finally the temperature of the cylindrical substrate (302) is controlled to a predetermined temperature of 50 ° C to 500 ° C.

A raw material gas for forming a deposited film is supplied to a reaction vessel (30
1), the gas cylinder valve (341-
346), make sure that the leak valve (308) of the reaction vessel is closed, and check the inflow valve (351-3).
56), the outflow valves (361 to 366) and the auxiliary valve (380) are confirmed to be open, and then the main valve (309) is first opened to exhaust the reaction vessel (301) and the gas pipe (307). To do.

Next, the reading of the vacuum gauge (310) is about 5 × 10.
^{When the} pressure reaches ^-6 Torr, the auxiliary valve (380) and the outflow valve (361 to 366) are closed.

After that, each gas is introduced by opening the valves (341-346) by the gas cylinder (331-396), and each gas pressure (for example, 2 Kg / cm ² ) is adjusted by the pressure regulator (391-396). Next, the inflow valves (351 to 356) are gradually opened to introduce each gas into the mass flow controllers (371 to 376).

After the preparation for film formation is completed as described above, a charge injection blocking layer, for example, on the cylindrical substrate (302),
Each layer such as a photosensitive layer and a surface layer is formed.

When the cylindrical substrate (302) reaches a predetermined temperature, the necessary ones of the outflow valves (361 to 366) and the auxiliary valve (380) are gradually opened, and the gas cylinders (331 to 336) are brought to a predetermined temperature. Gas is introduced into the reaction vessel (301) through the gas introduction pipe (305).
Next, the mass flow controllers (371 to 376) are adjusted so that each raw material gas has a predetermined flow rate. At that time, the opening of the main valve (309) is adjusted while observing the vacuum gauge (310) so that the pressure in the reaction vessel (301) becomes a predetermined pressure of 1 Torr or less. When the internal pressure is stable, the RF power source (not shown) is set to a desired power, and the RF power is introduced into the reaction vessel (301) through the high frequency matching box (306) to cause RF glow discharge. The raw material gas introduced into the reaction vessel is decomposed by this discharge energy, and the cylindrical substrate (30
2) A predetermined deposited film containing silicon as a main component is formed on the surface. After forming a desired film thickness, R
The supply of F electric power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a desired light-receiving layer having a multilayer structure is formed.

Needless to say, all the outflow valves other than the necessary gas are closed when forming each layer, and each gas is supplied to the reaction vessel (301).
Inside, outflow valve (361-366) from reaction container (30
In order to avoid remaining in the piping leading to 1), the outflow valves (361 to 366) are closed and the auxiliary valve (38
0) is opened, the main valve (309) is fully opened, and the system is temporarily evacuated to a high vacuum, if necessary.

In order to make the film formation uniform, the cylindrical substrate (302) is rotated at a predetermined speed by a driving device (not shown) during the film formation.

Needless to say, the above-mentioned gas species and valve operation may be changed according to the conditions for forming each layer.

The heating method of the cylindrical substrate (302) may be any heating element having a vacuum specification, and more specifically, electric resistance heating elements such as a wound heater of a sheath heater, a plate heater, a ceramic heater, and the like, Examples thereof include heat-generating lamps such as halogen lamps and infrared lamps, and heat-generating bodies using a heat exchange means such as liquid or gas as a heat medium. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used. In addition to the above, a container dedicated to heating is provided in addition to the reaction container (301) to heat the cylindrical substrate (302), and then the cylindrical substrate (302) is transferred into the reaction container (301) in a vacuum. And the like are used.

Next, a method of manufacturing the electrophotographic photosensitive member formed by the μW-PCVD method will be described.

FIGS. 4A and 4B show an example of a deposited film forming apparatus for forming a deposited film of an electrophotographic photosensitive member by a microwave plasma CVD (hereinafter referred to as “μW-PCVD”) method. FIG. 5 is a schematic configuration diagram, and FIG. 5 is an explanatory diagram of a state in which a source gas pipe is connected to the deposited film forming apparatus of FIG.

This apparatus comprises a reaction vessel (401) having a vacuum airtight structure and capable of being depressurized, and a source gas supply device (3).
30), and an exhaust device (not shown) for reducing the pressure inside the reaction vessel. In the reaction vessel (401), a microwave introduction window formed of a material (for example, quartz glass, alumina ceramics, etc.) capable of efficiently transmitting microwave power to the reaction vessel and maintaining vacuum tightness ( 402), a microwave waveguide (4) connected to a microwave power source (not shown) via a stub tuner (not shown) and an isolator (not shown).
03), which is made of a material having a large thermal conductivity (404)
(A)) and a substrate holder (404) made of a material (404 (b)) having a small coefficient of thermal expansion and thermal conductivity.
A cylindrical substrate (40) on which a deposited film is to be formed.
5), a substrate heating heater (406), a source gas introduction pipe (407), and an electrode (408) for applying an external electric bias for controlling the plasma potential are installed, and the inside of the reaction vessel (401) is It is connected to a diffusion pump (not shown) through an exhaust pipe (411).

The source gas supply device (330) is made of SiH.
_{4, H 2, CH 4,} NO, B 2 H 6, SiF 4 and the like material gas cylinders (331-336) and valves (341-3
46, 351-356, 361-366) and a mass flow controller (371-376),
A cylinder of each source gas is connected to a gas introduction pipe (407) in the reaction container via a valve (380). Also,
A space (42) surrounded by a cylindrical substrate (405)
0) forms the discharge space.

Formation of a deposited film in this apparatus by the μW-PCVD method can be performed as follows.

First, in the reaction vessel (401), a substrate made of a material having a large thermal conductivity (404 (a)) and a material having a small thermal expansion coefficient and a small thermal conductivity (404 (b)). The cylindrical substrate (405) mounted on the holder (404) is installed, the substrate (405) is rotated by the driving device (410), and the inside of the reaction container (401) is moved by an exhaust device (not shown) (for example, a vacuum pump). Exhaust pipe (411)
The pressure in the reaction vessel (401) is 1 × 1
Adjust to below 0 ^-6 Torr. Then, the heater for heating the substrate (406) is turned on. Then, the substrate holder (4
The inner surface of 04) directly receives the radiant heat from the heater (406) for heating the substrate. The heat received by the inner surface is transferred by heat conduction mainly inside (404 (a)) of the base body holder (404), and further, of the cylindrical base body (405) adhered to the surface of the base body holder (404). The temperature is transmitted to the inner surface and finally the temperature of the cylindrical substrate (405) is controlled to a predetermined temperature of 50 ° C to 500 ° C.

A raw material gas for forming a deposited film is supplied to a reaction vessel (40
1), the gas cylinder valve (341-
346), make sure that the leak valve (not shown) of the reaction vessel is closed, and check the inflow valve (351-3).
56), the outflow valves (361 to 366), and the auxiliary valve (380) are confirmed to be open, and then the main valve (not shown) is first opened to connect the inside of the reaction vessel (401) and the gas pipe (307). Exhaust.

Next, the reading of the vacuum gauge (not shown) is about 5 × 10.
^{When the} pressure reaches ^-6 Torr, the auxiliary valve (380) and the outflow valve (361 to 366) are closed.

Thereafter, the gas cylinders (331 to 336) introduce each gas by opening the valves (341 to 346), and the pressure regulators (391 to 396) adjust each gas pressure (for example, 2 Kg / cm ² ). Next, the inflow valve (3
51 to 356) are gradually opened to introduce each gas into the mass flow controller (371 to 376).

After the preparation for film formation is completed as described above, each layer such as the charge injection blocking layer, the photosensitive layer and the surface layer is formed on the cylindrical substrate (405).

When the cylindrical substrate (405) reaches a predetermined temperature, the necessary ones of the outflow valves (361 to 366) and the auxiliary valve (380) are gradually opened, and a predetermined amount is released from the gas cylinders (331 to 336). Gas is introduced into the discharge space (420) in the reaction vessel (401) through the gas introduction pipe (407). Next, the mass flow controllers (371 to 376) are adjusted so that each raw material gas has a predetermined flow rate. At that time, the opening of the main valve (not shown) is adjusted while observing the vacuum gauge (not shown) so that the pressure in the discharge space (420) becomes a predetermined pressure of 1 Torr or less. After the pressure is stabilized, a microwave power source (not shown) is used to set the frequency to 500 MHz or higher, preferably 2.
A microwave of 45 GHz is generated, a microwave power source (not shown) is set to a desired power, a waveguide (403),
Through the microwave introduction window (402), the discharge space (42
ΜW energy is introduced into 0) to cause μW glow discharge. Simultaneously with this, an electric bias such as direct current is applied from the power source (409) to the electrode (408). Thus, in the discharge space (420) surrounded by the substrate (405), the introduced source gas is excited by the energy of microwaves and dissociated to form a predetermined deposited film on the cylindrical substrate (405). . At this time, a motor for rotating the substrate (410) to achieve uniform layer formation
To rotate at a desired rotation speed.

After the desired film thickness is formed, the supply of μW electric power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction container, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a desired light-receiving layer having a multilayer structure is formed.

Needless to say, all the outflow valves other than the necessary gas were closed when forming each layer, and each gas was supplied to the reaction vessel (401).
Inside, outflow valve (361-366) from reaction container (40
In order to avoid remaining in the piping leading to 1), the outflow valves (361 to 366) are closed and the auxiliary valve (38
0) is opened, the main valve (not shown) is fully opened, and the system is once evacuated to a high vacuum as necessary.

It goes without saying that the above-mentioned gas species and valve operation may be changed according to the conditions for forming each layer.

The heating method of the cylindrical substrate (405) may be any heating element having a vacuum specification, and more specifically, electric resistance heating elements such as a wound heater of a sheath heater, a plate heater, a ceramic heater, and the like, Examples thereof include heat-generating lamps such as halogen lamps and infrared lamps, and heat-generating bodies using a heat exchange means such as liquid or gas as a heat medium. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used. In addition to the above, a container dedicated to heating is provided in addition to the reaction container (401) to heat the cylindrical substrate (405), and then the cylindrical substrate (405) is transferred into the reaction container (401) in a vacuum. And the like are used.

In the μW-PCVD method, in the discharge space
The pressure is preferably 1 × 10^-3Torr or more 1
× 10^-1Torr or less, more preferably 3 × 10^-3To
rr or more 5 × 10^-2Torr or less, most preferably 5 ×
10^-3Torr or more 3 × 10 ^-2Set below Torr
Is desirable.

The pressure outside the discharge space may be lower than the pressure inside the discharge space, but the pressure inside the discharge space is 1 × 10 ⁻¹ T.
Below orr, and most notably, 5 × 10 ^-2 Torr
Below, when the pressure inside the discharge space is three times or more the pressure outside the discharge space, the effect of improving the characteristics of the deposited film is particularly large.

As a method for introducing microwaves to the reaction furnace, a method using a waveguide can be mentioned. For introduction into the reaction furnace,
One method is to introduce through one or more dielectric windows. At this time, materials for the microwave introduction window into the furnace include alumina (Al ₂ O ₃ ), aluminum nitride (Al
N), boron nitride (BN), silicon nitride (SiN), silicon carbide (SiC), silicon oxide (SiO ₂ ), beryllium oxide (BeO), Teflon, polystyrene, and other materials with low microwave loss are usually used. .

The electric field generated between the electrode (408) and the cylindrical substrate (405) is preferably a DC electric field, and the direction of the electric field is more preferably directed from the electrode (408) to the cylindrical substrate (405). An electrode (40
The average magnitude of the DC voltage applied to 8) is 15 V or more and 300 V or less, preferably 30 V or more and 200 V or less. The DC voltage waveform is not particularly limited, and various waveforms are effective in the present invention. In other words, it does not matter in which case the direction of the voltage does not change with time. For example, not only the constant voltage whose magnitude does not change with time but also the pulse voltage and the magnitude rectified by the rectifier Is effective even when the pulsating voltage changes.

It is also effective to apply an AC voltage. There is no problem with the alternating current frequency,
Practically, 50 Hz or 60 Hz is suitable for low frequencies and 13.56 MHz is suitable for high frequencies. The AC waveform may be a sine wave, a rectangular wave, or any other waveform,
The sine wave is suitable for practical use. However, at this time, the voltage means an effective value in any case.

The electrode (408) may have any size and shape as long as it does not disturb the discharge, but in practical use, a cylindrical shape having a diameter of 0.1 cm or more and 5 cm or less is preferable. At this time, the length of the electrode (408) can also be arbitrarily set as long as the electric field is uniformly applied to the substrate.

The material of the electrode (408) may be any as long as it has a conductive surface, for example,
Stainless steel, Al, Cr, Mo, Au, In, Nb, T
Metals such as e, V, Ti, Pt, Pd, and Fe, alloys of these, or glass whose surface is electrically treated, ceramics, plastics, etc. are usually used.

In the present invention, when pre-cleaning is performed, it is particularly preferable to clean an aqueous system containing a surfactant and the like. When water-based cleaning is performed, the water quality before dissolving the surfactant may be any, but semiconductor grade pure water, particularly ultra LSI grade ultrapure water is particularly desirable. Specifically, the lower limit is 1 MΩ as the resistivity when the water temperature is 25 ° C.
-Cm or more, preferably 3 MΩ-cm or more, optimally 5
MΩ-cm or more is suitable for the present invention. The upper limit can be any value up to the theoretical resistance value (18.25 MΩ-cm), but from the viewpoint of cost and productivity, it is 17 MΩ-cm or less, preferably 15 MΩ-cm or less, and most preferably 13 MΩ-cm.
-Cm or less is suitable for the present invention. As the amount of fine particles, 0.2 μm or more is 10000 or less, preferably 1000 or less, and optimally 100 or less in 1 ml, which is suitable for the present invention. As the amount of microorganisms, the total number of viable bacteria is 100 or less, preferably 10 in 1 ml.
Less than or equal to 1 and optimally less than or equal to 1 are suitable for this invention. The amount of organic matter (TOC) per liter is 10 mg or less, preferably 1 mg or less, and most preferably 0.2 mg or less is suitable for the present invention.

As a method for obtaining the above-mentioned water of water quality, there are an activated carbon method, a distillation method, an ion exchange method, a filter filtration method, a reverse osmosis method, an ultraviolet sterilization method and the like. It is desirable to improve the quality of the water used.

If the temperature of the water is too high, an oxide film will be formed on the substrate, which may cause peeling of the deposited film. Also,
If it is too low, the cleaning effect is small and the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of water is 10 ° C or higher and 90 ° C or lower, preferably 20 ° C or higher and 75 ° C or lower,
Optimally, 30 ° C or higher and 55 ° C or lower is suitable for the present invention.

The surfactant used in the pre-washing step in the present invention is an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or a mixture thereof. Either one is possible.
Among them, anionic surfactants such as carboxylate, sulfonate, sulfate ester salt, and phosphate ester salt, or
Nonionic surfactants such as fatty acid esters are particularly effective in the present invention. As the builder, it is effective to use phosphate, carbonate, silicate, borate and the like. Examples of chelating agents include gluconate, EDTA, NTA,
It is effective to use a phosphate or the like.

In the present invention, the use of ultrasonic waves in the pre-cleaning step is effective in producing the effect of the present invention. The ultrasonic frequency is preferably 100 Hz or higher and 10 MHz or lower, more preferably 1 kHz or higher and 5 MHz or lower, and optimally 10 kHz or higher and 100 kHz or lower.
The output of ultrasonic waves is preferably 0.1 W / liter or more,
1 kW / liter or less, more preferably 1 W / liter or more and 100 W / liter or less is effective.

In the present invention, the water quality of the water used in the washing step with water containing dissolved carbon dioxide is very important.
Ultra pure water of ultra LSI grade is particularly desirable. Specifically, the lower limit of the resistivity when the water temperature is 25 ° C is 1 MΩ-
cm or more, preferably 3 MΩ-cm or more, optimally 5 M
Ω-cm or more is suitable for the present invention. The upper limit of the resistance value can be any value up to the theoretical resistance value (18.25 MΩ-cm), but 17 MΩ-c from the viewpoint of cost and productivity.
m or less, preferably 15 MΩ-cm or less, optimally 13
MΩ-cm or less is suitable for the present invention. As the amount of fine particles, 0.2 μm or more is 10000 in 1 ml.
Less than or equal to 100, preferably less than or equal to 1000, and optimally less than or equal to 100 is suitable for the present invention. As the amount of microorganisms, the total number of viable bacteria is 100 or less in 1 ml, preferably 1
0 or less, optimally 1 or less is suitable for the present invention.
The amount of organic matter (TOC) is 10 mg or less per liter,
Preferably 1 mg or less, optimally 0.2 mg or less is suitable for the present invention.

As a method for obtaining the above-mentioned water of water quality, there are an activated carbon method, a distillation method, an ion exchange method, a filter filtration method, a reverse osmosis method, an ultraviolet sterilization method, and the like. It is desirable to improve the quality of the water used.

The present invention is possible with any amount of carbon dioxide which dissolves in water up to the saturation solubility, but when it is too large, bubbles are generated when the water temperature fluctuates and adhere to the surface of the substrate to cause spots. The stain may occur. Further, when the amount of dissolved carbon dioxide is large, the pH becomes low, which may damage the substrate. on the other hand,
If the amount of dissolved carbon dioxide is too small, the effect of the present invention cannot be obtained.

Considering the quality required for the substrate,
It is necessary to optimize the amount of carbon dioxide dissolved according to the situation.

Generally, the preferred amount of carbon dioxide dissolved according to the present invention is 60% or less of the saturated solubility, more preferably 4% or less.
The condition is 0%.

In the present invention, it is practical to control the dissolved amount of carbon dioxide by the conductivity or pH of water, but when controlled by the conductivity, the preferable range is 2 μS / cm or more and 40 μS / cm or less, Preferably 4 μS / cm
Above, 35μS / cm or less, 6μS / cm or more, 30μ
When controlled by S / cm or less and pH, the preferable range is 3.8 or more and 6.0 or less, more preferably 4.0 or more,
The effect of the present invention is remarkable when the value is 5.0 or less. Conductivity is measured with a conductivity meter and the value is 2 by temperature correction.
The value converted to 5 ° C. is used.

If the temperature of water is too high, an oxide film will be formed on the substrate, which will cause the deposited film to peel off. Also,
If it is too low, the cleaning effect is small and the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of water is 10 ° C or higher and 90 ° C or lower, preferably 20 ° C or higher and 75 ° C or lower,
Optimally, 30 ° C or higher and 55 ° C or lower is suitable for the present invention.

The method of dissolving carbon dioxide in water may be a method of bubbling, a method of using a diaphragm, or the like. In the present invention, it is important to use water in which carbon dioxide is dissolved, and when a carbonate such as sodium carbonate is used to obtain carbonate ion, a cation such as sodium ion inhibits the effect of the present invention. Will end up.

When the surface of the substrate is washed with the water thus obtained in which carbon dioxide is dissolved, there are a method of washing by dipping, a method of applying water pressure and spraying.

In the case of cleaning by dipping, it is basically necessary to immerse the substrate in a water tank in which water in which carbon dioxide is dissolved is introduced. At that time, ultrasonic waves are applied, a water flow is given, air or the like is introduced. Therefore, the present invention becomes more effective when bubbling is used together.

When spraying, if the water pressure is too low,
The effect of the present invention was small and was obtained when it was too strong.
On the image of the electrophotographic photoreceptor, especially on the halftone image
A pear-skin-like pattern occurs. For this reason,
Is 2 kgf / cm² Above, 300kgf / cm
² Below, preferably 10kg · f / cm² More than 200
kgf / cm² Below, optimally 20kgf / cm² 
Above 150kgf / cm² The following are suitable for the present invention
There is. However, the pressure unit in the present invention is kg · f / cm² 
Means gravity kilobram per square centimeter, 1
kgf / cm ² Is equal to 98066.5 Pa.

As a method of spraying water, there is a method of spraying water whose pressure is increased by a pump from a nozzle, or a method of mixing water pumped up by a pump with high-pressure air before the nozzle and spraying it by the pressure of air. .

From the effect of the invention and economical efficiency, the flow rate of water is 1 liter / min or more and 200 liters / min or less, preferably 2 liters / min or more and 100 liters / min or less, per substrate, from the viewpoint of the effect of the invention and economical efficiency. Is 5 liter / min or more and 50 liter / min or less is suitable for the present invention.

If the temperature of water is too high, an oxide film will be formed on the substrate, causing the deposited film to peel off, and the effect of the present invention cannot be sufficiently obtained. Further, it is difficult to stably dissolve carbon dioxide in water. Conversely,
Even if it is too low, the effect of the present invention cannot be sufficiently obtained. Therefore, the temperature of water is 5 ° C or higher and 90 ° C or lower, preferably 10 ° C or higher and 55 ° C or lower, and most preferably 15 ° C.
C. or higher and 40.degree. C. or lower is suitable for the present invention.

If the treatment time of the cleaning treatment with water in which carbon dioxide is dissolved is too long, an oxide film is generated on the substrate, and if it is too short, the effect of the present invention is small, so that the treatment time is 10 seconds or longer and 30 minutes or shorter. Preferably 20 seconds or more, 20 minutes or less,
Optimally, 30 seconds or more and 10 minutes or less are suitable for the present invention.

In the present invention, it is important to cut the surface of the substrate immediately before the formation of the deposited film in order to remove the influence of the oxide film on the surface of the substrate during the formation of the deposited film.

If the time from cutting to the cleaning treatment with water in which carbon dioxide is dissolved is too long, an oxide film will be generated again on the surface of the substrate, and if it is too short, the process will not be stable.
1 minute or more and 16 hours or less, preferably 2 minutes or more and 8 hours or less, optimally 3 minutes or more and 4 hours or less are suitable for the present invention.

If the time from the cleaning treatment with the water in which carbon dioxide is dissolved to the introduction into the deposited film forming apparatus is too long, the effect of the present invention will be small, and if it is too short, the process will not be stable, and therefore 1 minute or more. 8 hours or less, preferably 2 minutes or more and 4 hours or less, most preferably 3 minutes or more and 2 hours or less are suitable for the present invention.

In the drying step, any drying method such as warm air drying, vacuum drying and warm water drying is effective. Drying with warm water in which carbon dioxide is dissolved is particularly preferable for enhancing the effect of the present invention.

In the present invention, when hot-water drying is performed on water in which carbon dioxide is dissolved, the quality of the water used is very important. LSI grade ultrapure water is preferred. Specifically, the lower limit value is 1M as the resistivity when the water temperature is 25 ° C.
Ω-cm or more, preferably 3 MΩ-cm or more, most preferably 5 MΩ-cm or more is suitable for the present invention. The upper limit of the resistance value can be any value up to the theoretical resistance value (18.25 MΩ-cm), but 17 MΩ in terms of cost and productivity.
-Cm or less, preferably 15 MΩ-cm or less, most preferably 13 MΩ-cm or less is suitable for the present invention. As the amount of fine particles, 0.2 μm or more is 100 in 1 ml.
00 or less, preferably 1000 or less, optimally 10
Zero or less is suitable for the present invention. As for the amount of microorganisms,
A total viable cell count of 100 or less, preferably 10 or less, and optimally 1 or less per 1 ml is suitable for the present invention. The amount of organic matter (TOC) is 10 mg or less, preferably 1 mg or less, and optimally 0.2 mg or less per 1 liter is suitable for the present invention.

As a method for obtaining the above-mentioned water of water quality, there are an activated carbon method, a distillation method, an ion exchange method, a filter filtration method, a reverse osmosis method, an ultraviolet sterilization method and the like. It is desirable to improve the quality of the water used.

The present invention is possible with any amount of carbon dioxide which dissolves in water up to the saturation solubility, but when it is too large, bubbles are generated when the water temperature fluctuates and adhere to the surface of the substrate to cause spots. The stain may occur. Further, when the amount of dissolved carbon dioxide is large, the pH becomes low, which may damage the substrate. on the other hand,
If the amount of dissolved carbon dioxide is too small, the effect of the present invention cannot be obtained.

Taking into consideration the quality required for the substrate,
It is necessary to optimize the amount of carbon dioxide dissolved according to the situation.

Generally, the preferred dissolution amount of carbon dioxide according to the present invention is 60% or less of the saturated solubility, more preferably 4% or less.
The condition is 0%.

In the present invention, it is practical to control the dissolved amount of carbon dioxide by the conductivity or pH of water, but when controlled by the conductivity, the preferable range is 2 μS / cm or more and 40 μS / cm or less, Preferably 4 μS / cm
Above, 35μS / cm or less, 6μS / cm or more, 30μ
When controlled by S / cm or less and pH, the preferable range is 3.8 or more and 6.0 or less, more preferably 4.0 or more,
The effect of the present invention is remarkable when the value is 5.0 or less. Conductivity is measured with a conductivity meter and the value is 2 by temperature correction.
The value converted to 5 ° C. is used.

The method of dissolving carbon dioxide in water may be a method such as bubbling or a method using a diaphragm. In the present invention, it is important to use water in which carbon dioxide is dissolved, and when a carbonate such as sodium carbonate is used to obtain carbonate ion, a cation such as sodium ion inhibits the effect of the present invention. Will end up.

If the temperature of water is too high, an oxide film will be formed on the substrate, which will cause the deposited film to peel off. Also,
If it is too low, the drying becomes insufficient and the effect of the present invention cannot be obtained sufficiently. Therefore, the temperature of water is 30 ° C or higher and 90 ° C or lower, preferably 35 ° C or higher and 80 ° C or lower,
Optimally, 40 ° C or higher and 70 ° C or lower is suitable for the present invention.

The material for the substrate holder (200 (a)) may have a thermal conductivity of 150 (W / m · K) or more, and more preferably 200 (W / m · K) or more. Specifically, for example, W, Au, Ag, Al, Cu and the like can be mentioned, but from the viewpoint of cost, weight and stability, Al is preferable in practical use.

The material for the substrate holder (200 (b)) may have a thermal conductivity of 80 (W / m · K) or less, preferably 50 (W / m · K) or less. Also,
The coefficient of thermal expansion is preferably 20 (10 ^-6 K ^-1 ) or less. Specifically, metals such as Ti, Cr, Fe, stainless steel, and A
ceramics such as l ₂ O ₃ and MgO.Al ₂ O ₃ and
Glass and the like can be used, but Ti and stainless steel are preferable from the viewpoint of cost and durability. Regarding the electrically insulating material such as glass or ceramic, it is possible to use a material such as the surface of which a conductive treatment is performed for grounding of the substrate and the substrate holder.

Regarding the surface property of the substrate holder (200 (a)), a rough surface is preferred in order to increase the contact area with the substrate or the surface area to make heat radiation efficient. On the other hand, if the surface property is made too rough and the surface area is increased, the amount of dust increases and dust is easily generated. Therefore,
The surface property is a ten-point average roughness (Rz), preferably 5 to 90 μm, more preferably 10 to 70 μm. The surface property is preferably uniform over the entire inner surface, but there is no practical problem if the difference between the maximum value and the minimum value within the surface is within 70 μm.

Regarding the surface property of the substrate holder (200 (b)), it is preferable that the surface is smooth in order to reduce the surface area and heat radiation. Therefore, the surface property in terms of ten-point average roughness (Rz) is preferably 60 μm or less, more preferably 50 μm or less.

It is preferable to increase the surface area of the joint between (200 (a)) and (200 (b)) in order to obtain electrical conduction, but from (200 (a)) to (200 (b)).
It is preferable to reduce the surface area in order to suppress the heat conduction to the. Therefore, the surface property of the connecting portion is ten-point roughness (R
z) is preferably 1 μm or more and 100 μm or less.

The means for forming the substrate holder (200) is not particularly limited, but (200 (a)) and (200)
Examples of the method include forming (b)) by welding, screwing, cooling springs or the like. Moreover, you may use them together.

The base body holder (200 (a)) may be formed at least in a portion facing the base body, but it is preferable that the base body holder (200 (a)) is formed longer in the vertical direction than the base body in terms of uniformity. Therefore, the length of (200 (a)) is 100 to 100 when the length of the substrate is 100.
150 is preferable, and 100 to 120 is preferable in terms of cost.

The substrate holder (200 (b)) is provided at the upper part and / or the lower part of the substrate holder (200).
There is no particular limitation as long as a portion that comes into contact with the rotating shaft (205) or the like is formed, and when the volume of (200 (a)) is 100, 80 to 100 is preferable, and in terms of cost, weight and durability. 20-40 is more preferable. Further, in order to further transport the substrate holder, for example, a convex shape or a concave shape for chucking the substrate holder on the upper portion of the substrate holder, or (10) in FIGS.
When the handle part having a shape such as 6) is formed, a method of providing a container for heating only as shown in FIG. 5, heating the substrate, and then transporting the substrate into the reaction container in a vacuum is used. In this case, it is preferable for suppressing the escape of heat due to the contact between the moving mechanism and the handle portion, and also for suppressing the dust generation due to the thermal expansion.

The thickness of the substrate holder (200 (a)) is not particularly limited, but is preferably 0.5 to 30 mm in view of cost, handleability, strength and heating time, and 1 to 2
0 mm is more preferable.

The thickness of the substrate holder (200 (b)) is not particularly limited, but is preferably 0.5 to 30 mm, more preferably 1 to 20 mm in terms of cost, handleability and strength.

The substrate (201) and the substrate holder (200
It is desirable to make a gap with (a)) in contact with each other in order to improve heat conduction, but there may be an acceptable gap. In this case, the substrate (201) and the substrate holder (200
The distance from (a)) is preferably 5 mm or less, and more preferably 3 mm or less in terms of uniformity of characteristics.

In the present invention, any material can be used as the material of the substrate as long as it has aluminum as a matrix, but the effect of the present invention is remarkable when a material containing a silicon atom is used. In the present invention, the content of silicon atoms is preferably 1 ppm or more and 1 wt% or less, and more preferably 10 ppm or more and 0.1 wt% or less.

In the present invention, it is effective to contain magnesium in order to improve the workability of the substrate. The preferable magnesium content is 0.1 wt% or more and 10 wt% or less, and more preferably 0.2 wt% or more and 5 wt% or less.

Further, in the present invention, H, Li, Na, K, B
e, Ca, Ti, Cr, Mn, Fe, Co, Ni, C
u, Ag, Zn, Cd, Hg, B, Ca, In, C, S
i, Ge, Sn, N, P, As, O, S, Se, F, C
It is effective to include any substance such as 1, Br, I in aluminum. In addition, the substrate holder (200
It is preferable to contain the same kind of material as that of (a) from the viewpoint of uniformity because the volume change due to thermal expansion becomes equal and the adhesion to the substrate or the distance to the substrate is kept stable.

In the present invention, the substrate may have any shape, but a cylindrical one is most suitable for the present invention.
The size of the substrate is not particularly limited, but the diameter is practically 2
0 mm or more, 500 mm or less, length 10 mm or more, 10
It is preferably 00 mm or less.

In the case of a non-single crystal photoreceptor containing silicon, the source gas used for forming the deposited film is silane (SiH
₄ ), disilane (Si ₂ H ₆ ), silicon tetrafluoride (SiF
₄ ), amorphous silicon forming raw material gas such as disilicon hexafluoride (Si ₂ F ₆ ) or a mixed gas thereof.

Examples of the diluent gas include hydrogen (H ₂ ), argon (Ar), helium (He) and the like.

Further, the band gap width of the deposited film is changed.
Nitrogen (N₂ ),ammonia
(NH₃ ) And other elements containing a nitrogen atom, oxygen (O₂ ),one
Nitric oxide (NO), nitrogen dioxide (NO₂ ), Nitrous oxide
(N₂ O), carbon monoxide (CO), carbon dioxide (CO
₂ ) Element containing oxygen atom such as methane (CH_Four ), Ethane
(C₂ H₆ ), Ethylene (C₂ H_Four ), Acetylene (C
₂ H₂ ), Propane (C ₃ H₈ ) Etc. monovalent hydrogen, tetrafluoride
Germanium (GeF_Four ), Nitrogen fluoride (NF₃ ) Etc.
An elementary compound or a mixed gas thereof may be used.

Further, in the present invention, diborane (B ₂ H ₆ ) and boron fluoride (BF) are used for the purpose of doping.
_{Even if} a dopant gas such as ₃ ) or phosphine (PH ₃ ) is introduced into the discharge space at the same time, the present invention is similarly effective.

In the electrophotographic photosensitive member of the present invention, the total film thickness of the deposited film on the substrate may be any, but 5 μm or more and 100 μm or less, and more preferably 10 μm or more and 7
When the thickness is 0 μm or less, and most preferably 15 μm or more and 50 μm or less, a particularly good image as an electrophotographic photosensitive member can be obtained.

In the present invention, the substrate temperature during deposition of the deposited film is effective in the range of 100 ° C. to 500 ° C., but particularly 150 ° C. to 450 ° C., preferably 20 ° C.
0 ° C or higher, 400 ° C or lower, optimally 250 ° C or higher, 35
A remarkable effect was confirmed at 0 ° C or lower.

In the present invention, the energy for generating plasma may be DC, RF, microwave or the like. Especially, when microwave is used as the energy for generating plasma, abnormal growth due to surface defects of the substrate is caused. Appears significantly and the absorbed water absorbs the microwave,
Since the change of the interface becomes more remarkable, the effect of the present invention becomes more remarkable.

The electrophotographic photosensitive member produced by the method of the present invention can be used not only in electrophotographic copying machines but also in electrophotographic applications such as laser beam printers, CRT printers, LED printers, liquid crystal printers and laser plate making machines. It can also be used widely.

The effects of the present invention will be specifically described below with reference to experimental examples, but the present invention is not limited to these.

[0208]

[Experimental example]

Experimental Example 1 Using the deposited film forming apparatus shown in FIG. 3, an amorphous silicon deposited film was formed on a substrate under the conditions shown in Table 1, and FIG.
A blocking type electrophotographic photoreceptor having the layer structure shown in (A) was produced.

In FIG. 8A, (801), (80
Reference numerals 2), (803), and (804) denote an aluminum substrate, a charge injection blocking layer, a photoconductive layer, and a surface layer, respectively. The substrate contains 100 ppm of silicon atoms
Made of aluminum, diameter 108 mm, length 358 m
A cylindrical substrate having a thickness of 5 mm and a wall thickness of 5 mm was subjected to surface cutting in the same procedure as the example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention.

In this experiment, an electrophotographic photosensitive member was prepared under the following six conditions. Condition 1 15 minutes after the end of the cutting process, cleaning with a detergent (nonionic surfactant) and cleaning with carbon dioxide-dissolved water were performed under the conditions shown in Table 2 by the surface treatment apparatus shown in FIG. However, at this time, as water in which carbon dioxide is dissolved, conductivity is 20 μS / cm and pH is approximately 4.2 by dissolving carbon dioxide in pure water having a resistivity of 10 MΩ · cm.
Water was used. After that, the cylindrical substrate was set on the substrate holder having the dimensions and shapes shown in Table 3A to prepare an electrophotographic photosensitive member. Condition 2 15 minutes after the end of the cutting process, cleaning with a detergent (nonionic surfactant) and cleaning with pure water were performed under the conditions shown in Table 4. The surface treatment apparatus shown in FIG. 1 was used, except that pure water that did not dissolve carbon dioxide was introduced into the cleaning tank (131). After that, the cylindrical substrate was set on the substrate holder having the dimensions and shapes shown in Table 3A to prepare an electrophotographic photosensitive member. Condition 3 15 minutes after the end of the cutting process, the substrate surface was treated under the conditions shown in Table 5 by the conventional substrate surface cleaning apparatus shown in FIG. The substrate cleaning apparatus shown in FIG. 9 comprises a processing tank (902) and a substrate transfer mechanism (903). The processing tank (902) is
It comprises a substrate loading table (911), a substrate cleaning tank (921), and a substrate unloading table (951). The cleaning tank (921) is equipped with a temperature control device (not shown) for keeping the temperature of the liquid constant. The transport mechanism (903) includes a transport rail (96
5) and the transfer arm (961), the transfer arm (9
61 is a moving mechanism (9) that moves on the rail (965).
62), a chucking mechanism (963) for holding the base body (901), and an air cylinder (964) for moving the chucking mechanism (963) up and down.

After cutting, the substrate (901) placed on the loading table (911) is washed by the transfer mechanism (903) into the cleaning tank (9).
21). Trichlorethane (trade name: ETERNA VG manufactured by Asahi Kasei Corporation) in the cleaning tank (921) (9
According to 22), cleaning is performed to remove the cutting oil and cutting chips adhering to the surface.

After cleaning, the substrate (901) is transferred to the transfer mechanism (9).
It is carried to the carry-out stand (951) by 03).

After that, the cylindrical substrate was set in the substrate holder having the dimensions and shapes shown in Table 3A to prepare an electrophotographic photosensitive member. Condition 4 15 minutes after the completion of the cutting process, cleaning with a detergent (nonionic surfactant) and cleaning with carbon dioxide-dissolved water were carried out under the conditions shown in Table 2 by the surface treatment apparatus shown in FIG. However, at this time, as water in which carbon dioxide is dissolved, conductivity is 20 μS / cm and pH is approximately 4.2 by dissolving carbon dioxide in pure water having a resistivity of 10 MΩ · cm.
Water was used. After that, the cylindrical substrate was set in the substrate holder having the dimensions and shapes shown in Table 3B to produce an electrophotographic photosensitive member. Condition 5 15 minutes after the end of the cutting process, cleaning with a detergent (nonionic surfactant) and cleaning with pure water were performed under the conditions shown in Table 4. The surface treatment apparatus shown in FIG. 1 was used, except that pure water that did not dissolve carbon dioxide was introduced into the cleaning tank (131). After that, the cylindrical substrate was set in the substrate holder having the dimensions and shapes shown in Table 3B to produce an electrophotographic photosensitive member.

The produced electrophotographic photosensitive member was installed in an electrophotographic apparatus which was modified from a Canon copying machine NP-6060 for high speed experiments, and the charging ability / charging ability unevenness, sensitivity / sensitivity unevenness, image density unevenness, white spots, etc. Was evaluated for electrophotographic characteristics. Further, the number of spherical projections generated on the surface of the photoconductor, the environmental property, and the surface condition of the inner surface of the substrate were evaluated.

Each item was evaluated by the following methods. Charging ability / charging ability unevenness An electrophotographic photoconductor is installed in the experimental device, and the charging device is + 6KV.
Is applied to carry out corona charging, and the surface potential of the electrophotographic photosensitive member is measured by the surface potential meter. The dark surface potential is measured every 3 cm from one end of the electrophotographic photosensitive member to the other end. 45 same measurement in the circumferential direction
Perform a total of 8 places in degrees. Then, the average of the obtained dark surface potentials is taken as the charging ability, and the variation (standard deviation) is taken as the charging ability unevenness. Sensitivity / uneven sensitivity The electrophotographic photoconductor is charged to a dark surface potential of 420V. Then, a certain amount of light is immediately emitted. The light image was emitted by using a xenon lamp light source and excluding light in a wavelength range of 550 nm or less using a filter. At this time, the surface potential of the bright portion of the electrophotographic photosensitive member is measured with a surface potential meter. 3 cm from one end of the electrophotographic photoreceptor to the other
The light surface potential is measured every other time. The same measurement is performed at a total of 8 places at 45 ° in the circumferential direction. Then, the average of the obtained light surface potentials is defined as sensitivity, and the variation (standard deviation) is defined as sensitivity unevenness.

At this time, the constant light quantity is 0.35 lx.sec.
And Image density unevenness Canon's halftone chart (Part number: FY9-904
2) with a circular area with a diameter of 0.05 mm as one unit on the copy image obtained when placing 2) on the platen and making a copy.
The image density at 00 points was measured, and the variation in the image density was evaluated.

◎: "Particularly good" ○: "Good" △: "No problem in practical use" ×: "There is a problem in practical use" White Poti Canon full black chart (part number: FY9-907
White spots having a diameter of 0.2 mm or less within the same area of the copy image obtained when 3) was placed on the platen and copied were evaluated.

⊚: “Particularly good” ○: “Good” Δ: “No problem in practical use” ×: “There is a problem in practical use” Number of spherical projections observed The entire surface of the electrophotographic photosensitive member was observed with an optical microscope to obtain 10
The number of spherical protrusions having a diameter of 15 μm or more in the area of 0 cm ² was examined. Environmental assessment ○ ... Do not use substances related to ozone depletion in the pretreatment process.

X: A substance relating to the destruction of the ozone layer is used in the pretreatment process. State of Inner Surface of Substrate The inner surface of the substrate was visually observed, and compared with the state of the inner surface before the formation of the deposited film, the evaluation was performed according to the following criteria.

⊚ indicates no change.

A slight discoloration is observed for the circles.

In Δ, discoloration is recognized in some places.

X has a large discoloration.

Table 6 shows the results thus obtained. In Table 6, the chargeability / chargeability unevenness, the sensitivity / sensitivity unevenness, and the number of spherical projections generated are relative evaluated with the result obtained under Condition 5 as 100.

As is clear from Table 6, the substrate is washed with water in which carbon dioxide is dissolved, and the base material is
(A) a material having a high thermal conductivity, (b) a material having a low coefficient of thermal expansion and a low thermal conductivity, at least a portion facing the substrate is composed of the material (a), and the upper and / or lower portion By using the substrate holder made of the material (b), it has become possible to produce an electrophotographic photoreceptor in which image defects and image density unevenness are significantly improved.

[0226]

[Table 1]

[0227]

[Table 2]

[0228]

[Table 3]

[0229]

[Table 4]

[0230]

[Table 5]

[0231]

[Table 6] Experimental Example 2 The amount of carbon dioxide dissolved in water was changed to examine the occurrence and correlation of image defects. Content of silicon atom is 100ppm
Made of aluminum, diameter 108mm, length 538m
The surface of a cylindrical substrate having a thickness of 5 mm and a thickness of 5 mm was cut by the same procedure as an example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention.

Fifteen minutes after the end of the cutting step, the surface treatment apparatus shown in FIG. 1 was used to perform washing with a detergent (nonionic surfactant) and water with carbon dioxide dissolved under the conditions shown in Table 2. However, at this time, as water in which carbon dioxide is dissolved, conductivity is changed from 0.1 μS / cm to 50 by dissolving carbon dioxide in pure water having a resistivity of 10 MΩ · cm.
Water adjusted to μS / cm was used.

After that, the cylindrical substrate is set on the substrate holder having the dimensions and shapes shown in Table 3A, and the deposited film forming apparatus shown in FIG. 3 is used to form an amorphous silicon deposited film on the substrate under the conditions shown in Table 3. Then, a blocking type electrophotographic photoreceptor having the layer structure shown in FIG. 8A was produced.

Table 7 shows the results of evaluation of the electrophotographic photosensitive member thus produced by the same method as in Experimental Example 1. Table 7
In, the chargeability, uneven chargeability, and the number of spherical projections
It is shown by relative evaluation when the conductivity is set to be 100 μS / cm (pure water only, CO _{2 is} not dissolved).

As is clear from Table 7, the electrophotographic photosensitive member produced by the method for producing an electrophotographic photosensitive member according to the present invention,
When the conductivity of the aqueous solution in which carbon dioxide was dissolved was in the range of 2 μS / cm to 40 μS / cm, a very good effect on image defects and the like was obtained.

[0236]

[Table 7] Experimental Example 3 After cutting an aluminum substrate in which the content of silicon atoms was changed in the same procedure as in Experimental Example 1, 15 minutes after the cutting process was completed, the surface treatment apparatus shown in FIG. Washing with water that dissolves carbon was performed. However, at this time, by dissolving carbon dioxide in pure water having a resistivity of 10 MΩ · cm, the conductivity is 20 μS / cm, and the pH is
The water was adjusted to about 4.2.

After that, the cylindrical substrate was set on the substrate holder having the dimensions and shapes shown in Table 3A, and the deposited film forming apparatus shown in FIG. 3 was used to form an amorphous silicon deposited film on the substrate under the conditions shown in Table 1. Then, a blocking type electrophotographic photoreceptor having the layer structure shown in FIG. 8A was produced.

Table 8 shows the results of evaluation of the electrophotographic photosensitive member thus produced by the same method as in Experimental Example 1. Table 8
As is clear from the above, in the electrophotographic photosensitive member manufactured by the method for manufacturing an electrophotographic photosensitive member according to the present invention, a very good effect on an image defect can be obtained in the range of containing 1 ppm to 1 wt% of silicon atom in aluminum of the substrate. It was

[0239]

[Table 8] Experimental Example 4 A substrate similar to that of Experimental Example 1 was cut by the same procedure, and 15 minutes after the cutting process was completed, the surface treatment apparatus shown in FIG.
The substrate surface was pretreated under the conditions shown in.

After that, the cylindrical substrate was set in the substrate holder having the dimensions and shapes shown in Table 3A, and the deposited film forming apparatus shown in FIG. 3 was used to form an amorphous silicon deposited film on the substrate under the conditions shown in Table 1. Then, a blocking type electrophotographic photoreceptor having the layer structure shown in FIG. 8A was produced.

In this experimental example, electrophotographic photoreceptors were manufactured by changing the quality (resistivity) of pure water used in the washing step with water in which carbon dioxide was dissolved. The electrophotographic photosensitive member thus obtained was evaluated in the same manner as in Experimental Example 1. For evaluation, 10 electrophotographic photoconductors produced under the same production conditions were evaluated, and the obtained evaluation results are shown in Table 9. However, the black stains and costs in the table were evaluated according to the following criteria. An image was output so that the average density of the image obtained by placing the full-half halftone original on the original plate was 0.4 ± 0.1 while changing the process speed for evaluating black spots . Among the image samples thus obtained, the one with the most noticeable stain was selected and evaluated. As an evaluation method, these images are 40 cm from the eyes.
Observe at a distance to see if there are any black spots,
The evaluation was performed according to the following criteria.

A: No black spots are observed on any of the copies.

◯: Some black spots were observed.

[0244] However, it is slight and there is no problem at all.

Δ: Black spots are recognized on any copy.

However, it is slight and practically no problem.

X: Large black spots are observed on all copies. Cost evaluation When obtaining the required amount of cleaning liquid ◎… Very affordable.

○: It is available at a low cost.

Δ: A little expensive.

X: expensive.

As is clear from Table 9, when the resistivity of pure water used in the washing step with water in which carbon dioxide is dissolved is 1 MΩ-cm or more before dissolving carbon dioxide, the electrophotographic photoreceptor manufacturing method of the present invention. The electrophotographic photosensitive member prepared by the above-mentioned method gave very good image quality.

[0252]

[Table 9] Experimental Example 5 A cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm made of aluminum having a silicon atom content of 100 ppm was used, and the same procedure as one example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention described above. The surface was cut with.

15 minutes after the completion of the cutting step, the surface treatment apparatus shown in FIG. 1 was used to perform washing with a detergent (nonionic surfactant) and washing with carbon dioxide dissolved water under the conditions shown in Table 2. However, at this time, as the water in which carbon dioxide was dissolved, water having a conductivity of 20 μS / cm and a pH of approximately 4.2 was used by dissolving carbon dioxide in pure water having a resistivity of 10 MΩ · cm.

Then, using the apparatus for manufacturing a photoreceptive member for electrophotography shown in FIG. 4, the above-mentioned cleaned cylindrical substrate was subjected to the microwave glow discharge method in accordance with the procedure detailed above, and shown in Table 10. A light-receiving member for electrophotography was produced under the production conditions.

At this time, a substrate holder having a shape shown in Table 3C was used. (I) Then, in Table 3C, aluminum having a thermal conductivity of about 240 (W / mK) is used for the 200 (a) part, and the thermal conductivity and the linear expansion coefficient of the 200 (b) part are changed. Let (II) In Table 3C, the 200 (b) part has a thermal conductivity of about 16 (W / mK) and a linear expansion coefficient of about 19 (10).
^-6 K ^-1 ) SUS was used, and the thermal conductivity of the 200 (a) part was changed.

The produced electrophotographic light-receiving member was placed in an electrophotographic apparatus obtained by modifying a Canon copying machine NP-6650 for high speed, and the electrophotographic characteristics such as charging ability and uneven sensitivity were evaluated. In addition, the number of spherical projections on the surface of the receiving member was evaluated.

Each item was evaluated by the following methods. Chargeability A current of 1000 μA is applied to the chargeability to carry out corona charging, and the surface potential of the dark part of the electrophotographic light-receiving member is measured with a surface potential meter. Sensitivity unevenness The photoreceptor member for electrophotography is charged to a dark surface potential of 420V. Then, a certain amount of light is immediately emitted. The light image is 550n using a xenon lamp light source and a filter.
Light excluding light in the wavelength range of m or less was irradiated. At this time, the surface potential of the light portion of the electrophotographic light-receiving member is measured with a surface potential meter. The bright surface potential is measured every 3 cm from one end to the other end of the electrophotographic light-receiving member. The same measurement is performed at a total of 8 places at 45 ° in the circumferential direction. And with the obtained variation (standard deviation) of the light surface potential,
The sensitivity is uneven.

At this time, the constant light quantity was 0.4 lx · sec. Number of Spherical Protrusions The entire surface of the electrophotographic light-receiving member was observed with an optical microscope to check the number of spherical protrusions having a diameter of 15 μm or more within an area of 100 cm ² .

The result thus obtained is (I)
Is shown in Table 11 and (II) is shown in Table 12. In Tables 11 and 12, each evaluation item is 200 (a) and 200.
Relative evaluation was carried out with 100 when aluminum having a thermal conductivity of about 240 (W / mK) and a linear expansion coefficient of about 25 (10 ^-6 K ^-1 ) was used for (b), and the results are shown below Classified as follows.

[0260] As is clear from the results of Tables 11 and 12, 200
In the part (a), the thermal conductivity is 150 (W / m · K) or more, and in the part (b), the thermal conductivity is 10 or more.
0 (W / mK) or less and a linear expansion coefficient of 20 (10
It was found that by forming the light receiving member using a substrate holder having a size of ^-6 K ^-1 ) or less, the charging ability is improved, and the uneven sensitivity and the number of spherical projections are reduced. Also, 200
In the part (b), the thermal conductivity of 50 (W / m · K) or less is more preferable, and in the part (a) of 200, the thermal conductivity of 200 (W / m · K) or more is more preferable. I knew it was.

Furthermore, in the substrate holder used above, N
For o1, 2, and 3, electrophotographic light-receiving members were produced 30 times in succession. At this time, after each film formation, the deposited film adhering to a part of the substrate holder was removed by liquid honing using glass beads, and the surface of the substrate holder was renewed for use. As a result, good results were obtained as in Table 2. However, No1 is 28th and No2 is 26
Since the resistance between the substrate holder and the rotating shaft increased the next time,
It has been found that it is more preferable to use a metal in terms of durability because the conductive treatment is performed again.

[0262]

[Table 10]

[0263]

[Table 11]

[0264]

[Table 12]

[0265]

EXAMPLES The constitution of the present invention was determined by the above experimental examples. Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. Example 1 A cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was made of aluminum having a silicon atom content of 100 ppm, was prepared by the same procedure as an example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention. The surface was cut with.

15 minutes after the end of the cutting process, the substrate was washed by the surface treatment apparatus shown in FIG. 1 under the conditions shown in Table 13. As the detergent, a mixture of a nonionic surfactant and an anionic surfactant was used.

After that, the cylindrical substrate is set on the substrate holder, and an amorphous silicon deposited film is formed on the substrate under the conditions shown in Table 14 by using the deposited film forming apparatus shown in FIG. An electrophotographic photosensitive member having a layer structure shown in FIG. In FIG. 8B, (801), (803),
(804) indicates an aluminum substrate, a photoconductive layer, and a surface layer, respectively.

As the substrate holder, (1) in Table 15 was used. The produced electrophotographic photoreceptor is installed in an electrophotographic apparatus that is a Canon copier NP-6060 modified for experimentation, and electrophotography of charging ability / uneven charging ability, sensitivity / unevenness of sensitivity, image density unevenness, white spots, etc. The characteristics were evaluated.

Each item was evaluated by the following methods. Chargeability / Chargeability unevenness The same evaluation as in Experimental Example 1 was performed. Sensitivity / uneven sensitivity The same evaluation as in Experimental Example 1 was performed. Image density unevenness The same evaluation as in Experimental Example 1 was performed. White spot Evaluation similar to that of Experimental Example 1 was performed.

Table 16 shows the results of these evaluations. In the table,
The chargeability / chargeability unevenness and the sensitivity / sensitivity unevenness are shown by relative evaluation with the result of Comparative Example 1 shown below as 100. Comparative Example 1 A cylindrical substrate made of aluminum having a silicon atom content of 100 ppm and having a diameter of 108 mm, a length of 358 mm and a wall thickness of 5 mm was used in the same manner as in the procedure of the method for producing an electrophotographic photosensitive member according to the present invention. The surface was cut according to the procedure.

15 minutes after the end of the cutting step, the substrate was washed with triethane under the conditions shown in Table 5 by the surface treatment apparatus shown in FIG.

After that, the cylindrical substrate is set on the substrate holder, and an amorphous silicon deposited film is formed on the substrate under the conditions shown in Table 14 by using the deposited film forming apparatus shown in FIG. An electrophotographic photosensitive member having a layer structure shown in FIG.

As the substrate holder, (4) in Table 15 was used.

The manufactured electrophotographic photosensitive member was evaluated in the same manner as in Example 1.

The evaluation results are shown in Table 16 together with Example 1.
Shown in.

The electrophotographic photosensitive member manufactured by the method for manufacturing an electrophotographic photosensitive member of the present invention showed very good results in all items as compared with the electrophotographic photosensitive member manufactured by the conventional method.

[0277]

[Table 13]

[0278]

[Table 14]

[0279]

[Table 15]

[0280]

[Table 16] Example 2 Diameter 80 m made of aluminum having a content of silicon atoms of 300 ppm and a content of magnesium atoms of 2 wt%.
The surface of a cylindrical substrate having a length of m, a length of 358 mm, and a wall thickness of 5 mm was cut by the same procedure as the procedure of the method for producing an electrophotographic photosensitive member according to the present invention.

15 minutes after the end of the cutting process, the substrate was washed under the conditions shown in Table 13 by the surface treatment apparatus shown in FIG. A nonionic surfactant was used as the detergent.

After that, the cylindrical substrate is set on the substrate holder, and an amorphous silicon deposited film is formed on the substrate under the conditions of Table 17 by using the deposited film forming apparatus shown in FIG. An electrophotographic photosensitive member having a layer structure shown in FIG. In FIG. 8C, (801), (802),
Reference numerals (803), (804), and (805) denote an aluminum substrate, an infrared absorption layer, a charge injection blocking layer, a photoconductive layer, and a surface layer, respectively.

As the substrate holder, (2) and (3) in Table 15 were used. The produced electrophotographic photoconductor is installed in an electrophotographic apparatus which is a Canon copier NP-9330 modified for high-speed experiments, and the chargeability / chargeability unevenness, sensitivity / sensitivity unevenness, image density unevenness, black spots, etc. The photographic characteristics were evaluated.

Each item was evaluated by the following methods. Chargeability / Chargeability unevenness The same evaluation as in Experimental Example 1 was performed. Sensitivity / uneven sensitivity The photoconductor for electrophotography is charged to a dark surface potential of 410V. Immediately, a constant amount of light (1.4 μJ / cm ² ) is applied. A spot type semiconductor laser of 80 μm (wavelength 780 nm) was used as a light source. At this time, the surface potential of the bright portion of the electrophotographic photoconductor is measured by a surface potential meter. 3c from one end to the other end of the electrophotographic photoconductor
The bright surface potential is measured every m. The same measurement is performed at a total of 8 places at 45 ° in the circumferential direction. Then, the average of the obtained light surface potentials is defined as sensitivity, and the variation (standard deviation) is defined as sensitivity unevenness. Image density unevenness The same evaluation as in Experimental Example 1 was performed. Black spots Black spots having a diameter of 0.2 mm or less within the same area of a copy image obtained by placing a white paper on a platen for copying were evaluated.

⊚ is “especially good” ○ is “good” Δ is “no problem in practical use” x is “problem in practical use” When evaluated in this way, all items are very good as in Example 1. The results were obtained.

[0286]

[Table 17] Example 3 A cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm, which was made of aluminum having a silicon atom content of 100 ppm, was used, and the same procedure as one example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention described above was performed. The surface was cut with.

15 minutes after the end of the cutting process, the substrate was washed by the surface treatment apparatus shown in FIG. 1 under the conditions shown in Table 13. As the detergent, a mixture of a nonionic surfactant and an anionic surfactant was used. After that, as the substrate holder, the same one as in Example 1 of the present invention and the same as that in Comparative Example 1 of the related art were used, and the apparatus for producing a light receiving member for electrophotography shown in FIG. An electrophotographic light-receiving member was produced on the cylindrical substrate by the microwave glow discharge method under the production conditions shown in Table 14 according to the procedure described in detail above. At this time, the distance between the base body and the base body holder was changed to manufacture. The chargeability and sensitivity unevenness of the produced electrophotographic light-receiving member were evaluated in the same manner as in Example 1, and the results shown in FIGS. 10 and 11 were obtained.

In FIG. 10, the horizontal axis represents the distance between the substrate and the substrate holder, and the vertical axis represents the charging ability. At this time, the vertical axis 10
0% indicates the charging ability of the electrophotographic light-receiving member produced at the same distance between the base and the base holder when the same base holder as in Comparative Example 1 was used.

In FIG. 11, the horizontal axis represents the distance between the substrate and the substrate holder, and the vertical axis represents the sensitivity unevenness. At this time, 1 on the vertical axis
00% shows the unevenness in sensitivity of the electrophotographic light-receiving member produced at the same distance between the base body and the base body holder when the same base body holder as in Comparative Example 1 was used. From these results, in the forming method of the present invention, the effect is remarkable when the distance between the substrate and the substrate holder is 5 mm or less, and particularly when the distance is 3 mm or less, it is more remarkable, and a certain effect is recognized as it is even if the distance is less than that. . Example 4 Diameter 80 m made of aluminum having a content of silicon atoms of 300 ppm and a content of magnesium atoms of 2 wt%.
The surface of a cylindrical substrate having a length of m, a length of 358 mm, and a wall thickness of 5 mm was cut by the same procedure as the procedure of the method for producing an electrophotographic photosensitive member according to the present invention.

15 minutes after the end of the cutting process, the substrate was washed under the conditions shown in Table 13 by the surface treatment apparatus shown in FIG. A nonionic surfactant was used as the detergent.
Thereafter, as the substrate holder, the same one as in Example 2 of the present invention was used, and the manufacturing apparatus for the electrophotographic light-receiving member shown in FIG. 3 was used, and on the cylindrical substrate, the procedure was described in detail above. A light-receiving member for electrophotography was produced by the high-frequency glow discharge method under the production conditions shown in Table 17. At this time, the distance between the base body and the base body holder was changed to manufacture. When the charging ability and sensitivity unevenness of the produced electrophotographic light-receiving member were evaluated, the same results as in Example 3 were obtained. Example 5 A cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm and made of aluminum having a silicon atom content of 100 ppm was used, and the same procedure as one example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention described above. The surface was cut with.

15 minutes after the end of the cutting process, the substrate was washed under the conditions shown in Table 13 by the surface treatment apparatus shown in FIG. As the detergent, a mixture of a nonionic surfactant and an anionic surfactant was used. After that, as the substrate holder, the same one as in Example 1 of the present invention and the same as that in Comparative Example 1 of the related art were used, and the apparatus for producing a light receiving member for electrophotography shown in FIG. An electrophotographic light-receiving member was produced on the cylindrical substrate by the microwave glow discharge method under the production conditions shown in Table 14 according to the procedure detailed above. At this time, the surface property (ten-point average roughness) of the substrate holder (200 (a)) was changed to fabricate. The charging ability, the sensitivity unevenness, and the number of generated spherical projections of the produced electrophotographic light-receiving member were evaluated in the same manner as in Example 1, and the results shown in FIGS. 12, 13 and 14 were obtained.

In FIG. 12, the horizontal axis is (200 (a)).
And the vertical axis represents charging ability. At this time, the vertical axis 10
0% shows the charging ability of the electrophotographic light-receiving member produced with the same surface property of (200 (a)) when the same substrate holder as in Comparative Example 1 was used.

In FIG. 13, the horizontal axis is (200 (a)).
The surface property of the part, and the vertical axis represents sensitivity unevenness. At this time, 1 on the vertical axis
00% shows uneven sensitivity of the electrophotographic light-receiving member produced with the same surface property of (200 (a)) when the same substrate holder as in Comparative Example 1 was used.

In FIG. 14, the horizontal axis is (200 (a)).
And the vertical axis represents the number of spherical projections generated. This time,
100% on the vertical axis represents the number of spherical projections generated in the electrophotographic light-receiving member produced with the same surface property of the (200 (a)) portion when the same substrate holder as in Comparative Example 1 was used.

From these results, the forming method of the present invention is
The surface property of the (200 (a)) part is remarkably 5 to 90 μm, and particularly remarkably effective when 10 μm to 70 μm. Example 6 Diameter 80 m made of aluminum having a content of silicon atoms of 300 ppm and a content of magnesium atoms of 2 wt%.
The surface of a cylindrical substrate having a length of m, a length of 358 mm, and a wall thickness of 5 mm was cut by the same procedure as the procedure of the method for producing an electrophotographic photosensitive member according to the present invention.

15 minutes after the end of the cutting process, the substrate was washed under the conditions shown in Table 13 by the surface treatment apparatus shown in FIG. A nonionic surfactant was used as the detergent.
After that, as the substrate holder, the same thing as in Example 2 of the present invention was used, and the manufacturing apparatus for the electrophotographic light-receiving member shown in FIG. 3 was used, and on the cylindrical substrate, according to the procedure detailed above, By the high frequency glow discharge method, a light receiving member for electrophotography was produced under the production conditions shown in Table 17. At this time, the surface property (ten-point average roughness) of the substrate holder (200 (a)) was changed to prepare the substrate. When the charging ability and sensitivity unevenness of the produced electrophotographic light receiving member were evaluated, Example 5 was obtained.
Similar results were obtained. Example 7 A cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm and made of aluminum having a silicon atom content of 100 ppm was used, and the same procedure as an example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention described above. The surface was cut with.

15 minutes after the end of the cutting process, the substrate was washed under the conditions shown in Table 13 by the surface treatment apparatus shown in FIG. As the detergent, a mixture of a nonionic surfactant and an anionic surfactant was used. Thereafter, as the substrate holder, the same one as in Example 1 of the present invention and the same as that in Comparative Example 1 of the related art were used, and a cylindrical shape was obtained by using the manufacturing apparatus for the electrophotographic light-receiving member shown in FIG. An electrophotographic light-receiving member was produced on the substrate by the microwave glow discharge method under the production conditions shown in Table 14 according to the procedure described in detail above. At this time, the photoconductive layer was manufactured by changing the internal pressure. The chargeability and sensitivity unevenness of the produced electrophotographic light-receiving member were evaluated in the same manner as in Example 1, and the results shown in FIGS. 15 and 16 were obtained.

In FIG. 15, the horizontal axis represents the internal pressure when producing the photoconductive layer, and the vertical axis represents the charging ability. At this time, 100% of the vertical axis
Shows the charging ability of the electrophotographic light-receiving member produced under the same internal pressure when the same substrate holder as in Comparative Example 1 was used.

In FIG. 16, the horizontal axis represents the internal pressure when producing the photoconductive layer, and the vertical axis represents the sensitivity unevenness. At this time, 100% of the vertical axis
Shows the sensitivity unevenness of the electrophotographic light-receiving member produced under the same internal pressure when the same substrate holder as in Comparative Example 1 was used.

From these results, the forming method of the present invention is
The lower the internal pressure, the more remarkable the effect compared to the conventional forming method,
In particular, when the pressure was 40 mTorr or less, it became more remarkable, and even at a pressure below that, a certain effect was observed as it was. Example 8 A cylindrical substrate having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm made of aluminum having a silicon atom content of 100 ppm was prepared by the same procedure as an example of the procedure of the method for producing an electrophotographic photosensitive member according to the present invention. The surface was cut with.

15 minutes after the end of the cutting step, the substrate was washed by the surface treatment apparatus shown in FIG. 1 under the conditions shown in Table 13. As the detergent, a mixture of a nonionic surfactant and an anionic surfactant was used. Thereafter, as the substrate holder, the same one as in Example 1 of the present invention and the same as that in Comparative Example 1 of the related art were used, and a cylindrical shape was obtained by using the manufacturing apparatus for the electrophotographic light-receiving member shown in FIG. An electrophotographic light-receiving member was produced on the substrate by the microwave glow discharge method under the production conditions shown in Table 14 according to the procedure described in detail above. At this time, the photoconductive layer was manufactured by changing the bias voltage. The charging ability and sensitivity unevenness of the produced electrophotographic light-receiving member were evaluated in the same manner as in Example 1, and the results shown in FIGS. 17 and 18 were obtained.

In FIG. 17, the horizontal axis represents the bias voltage during the production of the photoconductive layer, and the vertical axis represents the charging ability. At this time, 1 on the vertical axis
00% indicates the chargeability of the electrophotographic light-receiving member produced with the same bias voltage when the same substrate holder as in Comparative Example 1 was used.

In FIG. 18, the horizontal axis represents the bias voltage when the photoconductive layer was formed, and the vertical axis represents the sensitivity unevenness. At this time, 100% on the vertical axis represents the unevenness in sensitivity of the electrophotographic light-receiving member produced with the same bias voltage when the same substrate holder as in Comparative Example 1 was used.

From these results, the forming method of the present invention is
When the bias voltage is 20 (V) or more and 110 (V) or less, a remarkable effect is seen as compared with the conventional forming method.

[0305]

As described above, according to the present invention,
In a method for manufacturing an electrophotographic photosensitive member including a step of forming a functional film on an aluminum substrate, a non-single-crystal deposited film containing silicon atom and one or both of hydrogen atom and fluorine atom, particularly on the aluminum substrate. In a method for manufacturing an electrophotographic photosensitive member including a step of forming a film by a plasma CVD method, a substrate whose surface is washed with water in which carbon dioxide is dissolved, and a base material are (a) a material having a large thermal conductivity, (B)
A substrate made of a material having a small coefficient of thermal expansion and thermal conductivity, at least a portion facing the substrate is made of the material of (a), and an upper portion or a lower portion of the substrate holder is made of the material of (b). By using the holder, it is possible to inexpensively and stably manufacture an electrophotographic photosensitive member that gives a uniform high-quality image.

[Brief description of drawings]

FIG. 1 is a schematic vertical cross-sectional view of a pretreatment apparatus used to carry out the electrophotographic photosensitive member manufacturing method of the present invention.

FIG. 2 is a schematic configuration diagram for explaining the configuration of a preferred embodiment of the method for forming a photoreceptor according to the present invention.

FIG. 3 shows an example of an apparatus for forming an electrophotographic photoreceptor according to the present invention, and is a schematic explanatory view of an apparatus for producing an electrophotographic photoreceptor by an RF glow discharge method.

FIG. 4 shows an example of an apparatus for forming an electrophotographic photosensitive member according to the present invention, and is a schematic explanatory view of an electrophotographic photosensitive member manufacturing apparatus by a μW glow discharge method; Is a side sectional view of the apparatus, and (B) is a cross-sectional view of
The cross-sectional view in X '.

5 shows an example of an apparatus for forming an electrophotographic photosensitive member according to the present invention, in which the electrophotographic photosensitive member manufacturing apparatus by the RF glow discharge method of FIG. 3 is replaced by the deposition apparatus of FIG. Schematic explanatory diagram.

FIG. 6 is a diagram showing an example of an apparatus for forming an electrophotographic photosensitive member.

FIG. 7 is a diagram showing an example of an apparatus for forming an electrophotographic photosensitive member.

FIG. 8 is a diagram showing a layer structure of an electrophotographic photosensitive member.

FIG. 9 is a schematic vertical sectional view of a cleaning apparatus for cleaning a substrate as a pretreatment for forming a deposited film in a conventional method.

FIG. 10 is a graph showing the relationship between the distance between the substrate and the substrate holder and the charging ability of the light receiving member in Example 3.

FIG. 11 is a graph showing the relationship between the distance between the substrate and the substrate holder and the sensitivity unevenness of the light receiving member in Example 3.

FIG. 12 shows a surface property of 200 (a) in Example 5,
The graph which shows the relationship with the chargeability of a light receiving member.

13 is a surface property of 200 (a) in Example 5, and FIG.
The graph which shows the relationship with the sensitivity unevenness of a light receiving member.

14 is a surface property of 200 (a) in Example 5, and FIG.
9 is a graph showing the relationship with the number of spherical projections on the light receiving member.

FIG. 15 is a graph showing the relationship between the internal pressure when forming a deposited film and the charging ability of a light receiving member in Example 7.

FIG. 16 is a graph showing the relationship between internal pressure when forming a deposited film and uneven sensitivity of the light receiving member in Example 7.

FIG. 17 is a graph showing the relationship between the bias voltage and the charging ability of the light receiving member in Example 8.

FIG. 18 is a graph showing the relationship between the bias voltage and the sensitivity unevenness of the light receiving member in Example 8.

[Explanation of symbols]

 101 Substrate 102 Processing Unit 103 Substrate Transfer Mechanism 111 Substrate Loading Table 121 Substrate Pre-Cleaning Tank 122 Pre-Cleaning Solution 131 Cleaning Tank with Water Dissolving Carbon Dioxide 132 Water Dissolving Carbon Dioxide 141 Drying Tank 142 Nozzle 151 Substrate Carrying Out 161 Transport Arm 162 Moving Mechanism 163 Chucking Mechanism 164 Air Cylinder 165 Rail 201 Base 202 Base Substrate Holder 203 Base Substrate Holder Inner Surface 204 Auxiliary Substrate 205 Heating Means 206 Stand 207 Transport Handle 208 Substrate Surface 300 RF Glow Discharge Deposition Device 301 Reaction Container 302 cylindrical substrate 303 substrate holder 304 substrate heating heater 305 source gas introduction pipe 306 matching box 307 source gas pipe 308 reaction vessel leak valve 309 main exhaust Valve 310 Vacuum gauge 330 Raw material gas supply device 331 to 336 Raw material gas cylinder 351 to 356 Gas inflow valve 361 to 366 Gas outflow valve 371 to 376 Mass flow controller 391 to 396 Pressure regulator 400 μW Deposition apparatus by glow discharge method 401 Reaction vessel 402 Microwave introduction window 403 Waveguide 404 Substrate holder 405 Cylindrical substrate 406 Heater for substrate heating 407 Source gas introduction pipe 408 Bias electrode 409 Bias power supply 410 Motor for substrate rotation 411 Exhaust pipe 420 Discharge space 601 Vacuum reaction vessel 602 Cathode electrode 603 Gate 604 Bottom wall 605 Insulator 606 Base body 607 Base body holder 608 Heater 609 Gas introduction pipe 610 Gas release hole 611 Gas valve 612 Gas supply device 613 Discharge Tubes 614 exhaust valve 615 exhaust device 616 power 801 base 802 processor 803 base transport mechanism 811 base-on stand 821 base cleaning tank 822 cleaning liquid 851 base unloading platform 861 transfer arm 862 moving mechanism 863 chucking mechanism 864 air cylinder 865 rail

Claims (12)

[Claims] 1. An electrophotographic photosensitive member comprising an aluminum substrate mounted on a substrate holder, and a functional film made of an amorphous material having silicon atoms as a base material formed on the surface of the substrate by a reduced pressure vapor deposition method. In the method, the substrate is washed with water in which carbon dioxide is dissolved, and the base material of the substrate holder has (a) a material having a large thermal conductivity and (b) a thermal expansion coefficient and a thermal conductivity. An electrophotographic photosensitive member comprising a small material, at least a portion facing the substrate is composed of the material (a), and an upper portion and / or a lower portion of the substrate holder is composed of the material (b). Body manufacturing method. 2. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the conductivity of water in which the carbon dioxide is dissolved is 2 μS / cm or more and 40 μS / cm or less. 3. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the pH of the water in which the carbon dioxide is dissolved is 3.8 or more and 6.0 or less. 4. The water in which the carbon dioxide is dissolved is water in which carbon dioxide is dissolved in pure water having a resistivity of 1 MΩ · cm or more, according to any one of claims 1 to 3. Manufacturing method of electrophotographic photosensitive member. 5. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the aluminum substrate is an aluminum substrate containing at least a small amount of silicon atoms. 6. The method for producing an electrophotographic photosensitive member according to claim 5, wherein the aluminum substrate is an aluminum substrate containing at least 1 ppm to 1 wt% of silicon atoms. 7. The thermal conductivity of (a) is 200 (W / m).
・ K) or more, the thermal conductivity of (b) is 50 (W /
m · K) or less, thermal expansion coefficient is 20 (10^-6K ^-1) Below
An electronic copy according to any one of claims 1 to 6.
Method of manufacturing true photoconductor. 8. The method for manufacturing an electrophotographic photosensitive member according to claim 7, wherein the materials (a) and (b) are metallic materials. 9. The method for producing an electrophotographic photosensitive member according to claim 7, wherein the surface of the substrate side of the portion composed of the material (a) has a ten-point average roughness of 10 μm or more and 70 μm or less. 10. The method for producing an electrophotographic photosensitive member according to claim 7, wherein the distance between the portion made of the material (a) and the substrate is 3 mm or less. 11. After heating a substrate in a vacuum container dedicated to heating, the substrate is moved to a reaction container in a vacuum, and a photoreceptive layer made of an amorphous material containing silicon atoms as a base material is formed on the surface of the substrate. 11. The method for manufacturing an electrophotographic photosensitive member according to claim 7, wherein the deposited film forming apparatus is used. 12. In the vacuum vapor deposition method, a cylindrical substrate mounted on a substrate holder is arranged so as to surround a discharge space in a reaction vessel that can be substantially sealed, and a microwave introducing means is provided. A microwave discharge plasma containing a reactant derived from the source gas and contributing to film formation is formed, and a bias voltage is applied to an electrode provided in the discharge space so that the surface of the substrate is in the discharge space and in the non-discharge space. 12. A method for forming a light-receiving layer made of an amorphous material containing silicon atoms as a base material on the surface of a base material while moving the base material so as to alternately pass through and. The method for producing an electrophotographic photosensitive member according to 1.