JP2002004049A - System and method for forming deposit film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a system and a method for forming a deposit film, by which a deposit film in which structural defects are suppressed and uniformity is improved can be formed over a large area. SOLUTION: In the deposit film forming system, a plurality of mounting parts for cylindrical substrates (A mm diameter) 105 are arranged at equal spaces on the same circumference so that the minimum distance d mm between the cylindrical substrates adjacent to each other satisfies A/3<=d and the configuration circle L mm of cylindrical substrates satisfies 2,000>=L, and further, a plurality of high frequency power introducing means 102A are arranged outside the configuration circles of the mounting parts. In the deposit film forming method, the cylindrical substrate 105 are arranged in the above-mentioned positions and the deposit film is formed by the RF plasma CVD method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for depositing a deposited film on a substrate, especially a functional film, particularly a deposited film used for a semiconductor device, an electrophotographic photosensitive member, an image input line sensor, an imaging device, a photovoltaic device and the like. The present invention relates to a forming apparatus and a forming method.

[0002]

2. Description of the Related Art Conventionally, as a method for forming a deposited film used for an element member used for a semiconductor device, a photoreceptor for electrophotography, a photovoltaic device, and other various electronic elements,
Vacuum evaporation, sprinkling, ion plating, thermal CVD, optical CVD, plasma CVD, etc.
Many are known, and devices for that purpose have been put to practical use.

[0003] Among them, a plasma CVD method, that is, a method in which a raw material gas is decomposed by direct current, high frequency, or microwave glow discharge to form a thin film deposition film on a substrate is preferable, and examples thereof include hydrogen and / or halogen. Amorphous silicon compensated by (hereinafter, “a-Si:
At present, practical use of such a method as formation of a deposited film (expressed as "H, X") is extremely advanced, and various apparatuses for this purpose have been proposed.

FIG. 2 is a view schematically showing an example of a deposition film forming apparatus by a VHF plasma CVD method using a VHF band high frequency as a power supply, specifically, an example of an electrophotographic photosensitive member manufacturing apparatus. (A) is a schematic sectional view, (b) is a schematic sectional view along the cutting line AA 'of (a).

This apparatus is roughly classified into a reaction vessel 201,
The apparatus comprises a source gas supply device (not shown) and an exhaust system for reducing the pressure inside the reaction vessel. In the exhaust system, an exhaust port 211 is integrally formed on a side surface of the reaction vessel.
Is connected to an exhaust device (not shown). Eight cylindrical substrates 205 on which a deposited film is formed in a reaction vessel 201
Are arranged at equal intervals on the same circumference. The source gas is supplied from a source gas supply unit 206 to a film forming space surrounded by the cylindrical substrate 205.

Each cylindrical substrate 205 is held by a rotating shaft 208 and is heated by a heating element 207. When the motor 209 is driven, the reduction gear 210
, The rotating shaft 208 rotates, and the cylindrical base 205 rotates around its central axis in the generatrix direction. VHF power is supplied from a VHF power supply 203 to a deposition space from an electrode 202 via a matching box 204. At this time, the cylindrical substrate 205 is maintained at the ground potential through the rotating shaft 208.

The source gas supply device is composed of SiH ₄ , GeH ₄ ,
It is composed of a source gas cylinder such as H ₂ , CH ₄ , B ₂ H ₆ , PH ₃ , a valve and a mass flow controller, and each source gas cylinder is connected to the source gas introduction means 206 in the reaction vessel via an auxiliary valve. Have been.

Using such a conventional deposited film forming apparatus, a deposited film can be formed by the following procedure.

First, a cylindrical substrate 20 is placed in a reaction vessel 201.
5 is installed, and the inside of the reaction vessel 201 is exhausted by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the heating element 20
7, the temperature of the cylindrical substrate 205 is controlled to a predetermined temperature of 200 to 450 ° C.

A source gas for forming a deposited film is supplied to a reaction vessel 201.
In order to allow the gas to flow into the reaction vessel 201, first make sure that the gas cylinder valve is closed, and make sure that the inflow valve, outflow valve, and auxiliary valve are open. Exhaust the gas piping. Next, when the reading of the vacuum gauge becomes about 6.7 × 10 ⁻⁴ Pa, the auxiliary valve and the outflow valve are closed. Thereafter, each gas is introduced from a gas cylinder by opening the cylinder valve, and each gas pressure is adjusted to about 2 kg / cm ² by a pressure regulator. Next, the inflow valve is gradually opened to introduce each gas into the mass flow controller.

When the temperature of the cylindrical substrate 205 reaches a predetermined temperature, necessary ones of the outflow valves and the auxiliary valve are gradually opened, and a predetermined gas is supplied from the gas cylinder into the reaction vessel 201 through the raw material gas introduction means 206. To be introduced. Next, each raw material gas is adjusted by a mass flow controller so as to have a predetermined flow rate. At that time, the reaction vessel 2
The opening of the exhaust valve is adjusted while looking at the vacuum gauge so that the pressure in 01 becomes a predetermined pressure of 1.3 × 10 ² Pa or less.

When the internal pressure is stabilized, the VHF power supply 20
3 is set to a desired power, and the matching box 20 is set.
4. VHF electric power is introduced into the reaction vessel 201 through the electrode 202 to generate glow discharge. The raw material gas introduced into the reaction vessel 201 is decomposed by the discharge energy, and a deposited film mainly containing predetermined silicon is formed on the cylindrical substrate 205. After the deposited film having a desired thickness is formed, the supply of the high-frequency power is stopped, the outflow valve is closed, the flow of gas into the reaction vessel 201 is stopped, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a desired photosensitive layer having a multilayer structure can be formed. In the formation of the multilayer film, a plurality of layers may be formed continuously by gradually changing the high-frequency power, gas flow rate, and pressure to the set values of the next layer within a certain time after the formation of one layer.

When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed.
In order to avoid remaining in the pipe from the outflow valve to the reaction vessel 201, it is necessary to close the outflow valve, open the auxiliary valve, and fully open the exhaust valve to once exhaust the system to a high vacuum. Perform according to. During the formation of the deposited film, the motor 209 is driven to reduce the speed of the reduction gear 210.
By rotating the rotating shaft 208 via the shaft and rotating the cylindrical substrate 205, a deposited film is formed over the entire surface of the cylindrical substrate.

When a deposited film having a large area, such as an electrophotographic photoreceptor, is formed in this way, it is necessary to form a uniform and high-quality deposited film and to improve reproducibility and productivity. Various device configurations have been proposed.

For example, in Japanese Patent Application Laid-Open No. 8-253865, a plurality of cylindrical substrates and a plurality of electrodes for applying high-frequency power are installed in a reaction vessel, and all electrodes surrounding one cylindrical substrate are substrates. A technique for improving productivity and uniformity of deposited film characteristics by arranging them at the same distance from each other is disclosed. Also, for example, Japanese Patent Application Laid-Open No. 63-241179 discloses that the thickness distribution is made uniform by optimizing the interval between a plurality of cylindrical substrates arranged on the same circumference so as to surround the discharge space of the microplasma. And techniques for improving film quality are disclosed. In addition, for example, in Japanese Patent Application Laid-Open No. 9-256160, a plurality of cylindrical substrates are arranged on the same circumference, and a plurality of cathode electrodes are arranged outside the arrangement circle.
There is disclosed a technique for greatly increasing the deposition film speed and improving the productivity.

With these techniques, the uniformity and characteristics of the electrophotographic photosensitive member have been improved, and accordingly, the yield has also been improved.

[0018]

However, the demand level in the market for products using these deposited films is increasing day by day, and in recent years, higher quality deposited films have been demanded in order to meet these demands. .

For example, in the case of an electrophotographic apparatus, there is a very strong demand for an improvement in copy speed, a reduction in the size of the electrophotographic apparatus, and a reduction in cost. In order to realize these, it is indispensable to improve the photoreceptor characteristics, specifically, charging ability, sensitivity and the like, and to reduce the photoreceptor production cost. In recent years, digital electrophotographic apparatuses and color electrophotographic apparatuses, which have been remarkably popularized, frequently copy not only text documents but also photographs, pictures, design pictures, etc., so that image density unevenness is reduced and ghost memory is reduced. Improvements in photoreceptor characteristics, such as reduction in image density, have been required more strongly than ever.

In order to improve the photoreceptor characteristics and reduce the production cost of the photoreceptor, one of the demands in the electrophotographic photoreceptor manufacturing technology is to improve the uniformity of the deposited film characteristics and to improve the deposited film characteristics. There is a strong need for a technique for suppressing variations. Further, as another demand, there is a demand for suppressing structural defects caused by dust adhering to the surface on which a deposited film is formed during film formation, which has not been a problem so far. In the following description, the term “structural defect” refers to a defect that has adhered to a foreign substance such as dust on a surface on which a deposited film is formed and has grown from the foreign substance.

In the case of an electrophotographic photosensitive member, for example, this structural defect is confirmed as a hemispherical projection (hereinafter, referred to as "spherical projection") on the photosensitive member. When such a spherical protrusion is present, when the photoreceptor is charged, the electric charge escapes from the spherical protrusion onto the substrate, and as a result, appears as a black spot or a white spot on the electrophotographic image, and the quality of the electrophotographic image is reduced. Is greatly impaired. Also, in the case of other electronic devices,
It hinders the movement of the carrier and causes a malfunction.

At present, in order to prevent such a quality problem, after the production process is completed, a strict inspection is performed to check a product to determine whether it is good or defective. Since the defective product rate at this time is directly linked to the production cost, techniques for suppressing such structural defects have been actively promoted.

However, due to the recent high performance of electronic devices and the demand for higher reliability from the market, the allowable level of such structural defects (the number of structural defects and the size of structural defects) is becoming severer year by year. . Under such circumstances, in order to achieve a further reduction in production cost, expectations for a technology for suppressing structural defects are increasing more than ever.

That is, an object of the present invention is to provide a deposited film forming apparatus and a deposited film forming method capable of forming a good deposited film with suppressed structural defects over a large area and improving the uniformity of the deposited film characteristics. is there.

[0025]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that the cylindrical substrate arranged on the same circumference can be shortest between adjacent cylindrical substrates. By optimizing the distance and the diameter of the arrangement circle of the cylindrical substrate, and introducing high-frequency power from an electrode installed outside the arrangement circle of the cylindrical substrate, structural defects are suppressed on the plurality of cylindrical substrates. It has been found that a deposited film having good characteristics can be formed uniformly, and the present invention has been completed.

That is, the present invention comprises a vacuum-tight airtight reaction vessel having a plurality of mounting portions for supporting the cylindrical substrate, and decomposes the raw material gas supplied into the reaction vessel and places the gas on the cylindrical substrate. In a deposited film forming apparatus for forming a deposited film,
When the diameter of the cylindrical substrate is Amm, the shortest distance dmm between adjacent cylindrical substrates satisfies A / 3 ≦ d,
And the diameter Lmm of the circle of arrangement of the cylindrical substrate is 2000 ≧ L
Wherein the plurality of mounting portions are arranged at equal intervals on the same circumference, and a plurality of high-frequency power introducing means are arranged outside the arrangement circle of the mounting portions. This is a deposition film forming apparatus.

Further, according to the present invention, each of the cylindrical substrates is supported on a plurality of mounting portions in a vacuum-tight airtight reaction vessel, and the raw material gas supplied into the reaction vessel is decomposed and deposited on the cylindrical substrate. In the method for forming a deposited film for forming a film, a plurality of the cylindrical substrates are arranged at equal intervals on the same circumference, and a plurality of high-frequency power introducing means are arranged outside the arrangement circle of the cylindrical substrates. When the diameter of the cylindrical substrate is Amm, the shortest distance dmm between the adjacent cylindrical substrates satisfies A / 3 ≦ d, and the diameter Lmm of the arrangement circle of the cylindrical substrate satisfies 2000 ≧ L. A method for forming a deposited film, comprising forming a deposited film.

The mechanism by which the generation of spherical projections and the variation in film properties are suppressed by the present invention has not been completely elucidated at present, but is presumed to be roughly as follows.

During film formation, dust generated due to film peeling or the like,
It passes through the sheath region formed around the electrode and reaches the surface of the deposited film on the cylindrical substrate. In the sheath region, a positive current (ion flow) or a negative current (electron flow) flows from the plasma into the cylindrical substrate, reflecting the plasma characteristics. The amount of dust that has been negatively charged up in the plasma changes due to the flow of current in the sheath region.

If the amount of charge of the dust when passing through the sheath region and reaching the surface of the cylindrical substrate is large, the dust adheres to the surface of the deposited film of the substrate at the ground potential by Coulomb force. After the deposition, the charge held by the dust flows into the cylindrical substrate through the deposited film and disappears, but at the same time, a new charge is stored by the current flowing from the plasma to the surface of the deposited film. Continue to adhere with. During this time, the formation of the deposited film proceeds, and it is considered that dust is eventually taken into the film and becomes the nucleus of the spherical projection.

On the other hand, when the amount of charge of the dust when passing through the sheath region and reaching the surface of the cylindrical substrate is small, the dust does not adhere due to Coulomb force, and no spherical projection occurs. The amount of dust charge-up upon reaching the cylindrical substrate is greatly affected by the amount of current flowing in the sheath region, that is, the plasma characteristics.

Based on the above-mentioned idea, the present inventors have made FIG.
The number of spherical projections on the surface of the substrate on which the deposited film was formed was observed using the deposited film forming apparatus shown in FIG. 3A and 3B are diagrams showing the results. FIG. 3A is a schematic cross-sectional view showing a positional relationship between an electrode and a cylindrical base, and FIG. 3B is a graph showing a correlation between a spherical projection ratio and a circumferential angle. Here, the cylindrical substrate 305 was stopped, and a deposited film was formed using the second electrode 302B provided in the circle where the cylindrical substrate 305 was arranged.

As shown in FIGS. 3A and 3B, a portion of the surface of the cylindrical substrate 305 in the direction of the second electrode (hereinafter referred to as “front portion”) is closer to the adjacent cylindrical substrate. 305
It has been clarified that spherical projections are concentrated on the shortest distance portion (hereinafter, referred to as “slope portion”). As a result, in order to make the plasma characteristics of the slope portion the same as the plasma characteristics of the front portion, by increasing the distance between adjacent cylindrical substrates 305, it is possible to achieve uniform plasma characteristics.
It has been further found that spherical projections can be reduced. Further, as a result of further study, the diameter of the cylindrical substrate was changed to Amm
When each cylindrical substrate is arranged such that the shortest distance dmm between adjacent cylindrical substrates satisfies A / 3 ≦ d,
It has been found that it is very effective in suppressing structural defects.

On the other hand, when the shortest distance d is increased, the diameter Lmm of the arrangement circle of the cylindrical base is increased accordingly. In this case, since the size of the reaction vessel is inevitably increased, the cost of the manufacturing apparatus is increased, and the productivity of the apparatus is significantly reduced. Here, it is conceivable to reduce the number of cylindrical substrates to be installed so that the diameter L does not increase. To decline. Therefore, as a result of further study in consideration of these points, as a result of disposing each cylindrical base so that the diameter Lmm of the arrangement circle of the cylindrical base satisfies 2000 ≧ L, the shortest distance dmm
It was also found that the correlation with the conditions was appropriate.
Regarding the number of installations, an optimum number of installations may be appropriately adopted within the range of these conditions while considering mass productivity.

Further, it is presumed that the mechanism for suppressing variations in film characteristics according to the present invention has the following points.

The characteristics of the plasma in the vicinity of the wall surface in contact with the plasma, specifically, the energy distribution of electrons are particularly different from those in other regions. For this reason, ions incident on the wall surface from the plasma are accelerated in the sheath region and collide with the wall surface in a high energy state. At this time, electrons are emitted from the wall surface, and the electrons are accelerated in the sheath region,
It becomes a high energy state and enters the plasma. As a result, the ratio of high-energy electrons near the wall surface is higher than in other regions, and it is considered that the type or ratio of active species generated there is different.

When a deposited film is formed on a cylindrical substrate, the surface of the substrate itself corresponds to the wall surface described above. Therefore, when a plurality of cylindrical substrates are arranged, the distribution of the plasma region having a high ratio of high-energy electrons differs depending on the arrangement. If this distribution shape for the cylindrical substrate is different for each cylindrical substrate, as described above, the type of the active species reaching the cylindrical substrate,
The ratios are different from each other, and it is considered that the characteristics of the deposited film formed by the active species are likely to vary among the substrates.

In the present invention, since the cylindrical substrates are arranged at equal intervals on the same circumference, the distribution shapes of the plasma regions having a high ratio of high energy electrons to each cylindrical substrate are all the same, and reach the substrate. The types and ratios of active species are the same on all substrates. As a result, the characteristics of the deposited film formed on the cylindrical substrate are also excellent with little characteristic variation between the substrates.

In the present invention, it is preferable that the frequency of the high-frequency power be in the range of 50 to 450 MHz, since the uniformity of the film characteristics in the circumferential direction of the cylindrical substrate is remarkably improved. In a frequency region lower than 50 MHz, the pressure at which plasma can be generated stably tends to increase rapidly. According to the study of the present inventors, for example, when the frequency is 1
In the case of 3.56 MHz, the pressure at which the plasma can be generated stably is about 1 compared with the case where the frequency is 50 MHz or more.
It has been confirmed that the figure is half an order of magnitude higher. At such a high pressure, fine particles such as polysilane are likely to be generated in the film forming space, and if the fine particles are taken into the deposited film, the film quality is deteriorated. These fine particles are likely to be generated particularly in the vicinity of the sheath, and it is considered that the fine particles are taken into the film between adjacent cylindrical substrates. In the present invention, since the frequency of the high-frequency power is set to 50 MHz or more,
Incorporation of fine particles into such a film becomes difficult,
It is considered that a good deposited film is formed over the entire circumference of the cylindrical substrate.

Further, even in a frequency region higher than 450 MHz, due to the difference in the uniformity of plasma, 450 MHz
The uniformity of the film characteristics is lower than in the following cases. In the frequency region where the frequency is higher than 450 MHz, the power absorption near the power introducing means is large, and electrons are generated most frequently there. Easy to connect. In the present invention,
Since a frequency of 450 MHz or less is used, extreme power absorption near the power introducing means is unlikely to occur, and plasma uniformity and
Furthermore, the uniformity of the film characteristics is significantly improved.

Further, in the present invention, it is preferable that a plurality of high-frequency power introducing means are arranged at equal intervals on the same circumference having the same center as the arrangement circle of the cylindrical substrate. In the plasma, the surface of the high-frequency power introduction means also acts as a wall surface, and affects the characteristics of the deposited film to be formed for the above-described reason. Therefore, by arranging as described above, the effect on each cylindrical substrate is made more uniform, and the effect of suppressing the characteristic variation between the substrates is further enhanced.

Further, in the present invention, a plurality of high-frequency power introducing means (first electrodes) arranged outside the circle where the cylindrical base is arranged, and the high-frequency power introducing means (first electrode) arranged inside the circle are arranged. It is preferable that the high-frequency power introduced from the first electrode and the high-frequency power introduced from the second electrode can be independently controlled. In this case, the film characteristics in the circumferential direction of the cylindrical substrate can be very strictly controlled, so that the film characteristics can be improved and the fluctuation in the film characteristics can be further suppressed.

Further, it is preferable to introduce high-frequency power from one oscillation source to the first electrode and the second electrode. When the oscillation sources are different, it is difficult to completely match the oscillation frequencies between the two power supplies, and the difference in the oscillation frequencies causes a phase difference to be changed during deposition film formation or for each deposition film formation lot. And, by this phase difference,
The type and ratio of active species generated in the plasma may change, and in some cases, the plasma may become unstable. Therefore, if a single transmission source is used as described above, variations in deposited film characteristics among lots can be more effectively suppressed.

Further, in the present invention, there is further provided a cylindrical wall member made of a non-conductive material disposed so as to surround the plurality of cylindrical substrates, and the central axis of the cylindrical wall member is the arrangement of the cylindrical substrates. It is preferable that the plurality of high-frequency power introducing means arranged through the center of the circle and outside the arrangement circle are located outside the cylindrical wall material. In this case, the loss of the raw material gas due to the film adhesion to the high frequency power introducing means is eliminated, the raw material gas use efficiency is improved, and the production cost can be reduced. Furthermore,
Since the film does not peel off from the surface of the high-frequency power supply means during the formation of the deposited film, dust in the film forming space is reduced, and defects in the deposited film can be suppressed.

Further, in the present invention, it is preferable that the source gas supply gas means for supplying the source gas is disposed inside and outside the arrangement circle of the cylindrical substrate. In this case, the characteristics of the deposited film can be further improved. This is based on the knowledge of the present inventors that the source gas supply position may greatly affect the characteristics of the deposited film.
When the source gas is supplied from the source gas supply unit into the film formation space, the source gas quickly spreads throughout the film formation space. However, also in this process, the source gas is decomposed by the high-frequency power, so that the gas composition varies depending on the distance from the source gas supply unit. For example, the raw material gas is the case of SiH _4, the decomposition of SiH ₄ with distance from the source gas supply means passes, SiH ₄ is reduced. Conversely, since the H ₂ produced by the decomposition of SiH ₄ increases as the distance from the source gas supply means, at a distance from the material gas supply means, a SiH ₄ which though was diluted _with H ₂ as if used as the raw material gas Deposited film characteristics will result. Such a phenomenon is particularly remarkable when high-frequency power is large or when high-frequency power in a frequency band with high raw material gas decomposition efficiency is used. Therefore, if the source gas supply means is arranged inside and outside the arrangement circle of the cylindrical substrate, the above-described problems are substantially avoided, and the desired characteristics can be obtained in all regions of all the cylindrical substrates. This makes it possible to form a deposited film.

[0046]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below.

FIG. 1 shows an apparatus for forming a deposited film by a high-frequency plasma CVD method according to the present invention (a manufacturing apparatus for an a-Si photosensitive member).
1A is a schematic cross-sectional view showing one embodiment of the present invention, in which FIG. 1A is a schematic cross-sectional view, and FIG. 1B is a schematic cross-sectional view along a cutting line AA ′ in FIG.

This apparatus is roughly classified into a reaction vessel 101,
The apparatus comprises a source gas supply device (not shown) and an exhaust system for reducing the pressure inside the reaction vessel. Exhaust system is reaction vessel 1
An exhaust port 111 is integrally formed on a side surface of the exhaust port 01, and the other end of the exhaust port 111 is connected to an exhaust device (not shown).

The cylindrical substrate 105 on which the deposited film is formed is
A plurality (six) are arranged at equal intervals on the same circumference having a diameter Lm by being supported by predetermined mounting portions. When the diameter of the cylindrical substrate 105 is Am, the shortest distance dmm between the adjacent cylindrical substrates 105 satisfies A / 3 ≦ d, and the diameter Lm of the arrangement circle of the cylindrical substrate 105 is 200.
0 ≧ L is satisfied. The mounting portions that support the cylindrical substrate 105 are arranged at equal intervals on the same circumference. Usually, in order to arrange the cylindrical substrates 105 at equal intervals on the same circumference, an apparatus configuration in which the mounting portions for supporting the cylindrical substrates 105 are similarly arranged may be used. In the following description, the position of the cylindrical base 105 will be mainly described, but at the same time, it can be said that the position of the mounting portion is also described with respect to the apparatus configuration.

The raw material gas supply means 106 includes the cylindrical substrate 1
05 are arranged inside and outside the circle. Outside the arrangement circle, a plurality of (six) source gas supply means 106 are arranged at equal intervals on the same circumference (concentric with the arrangement circle of the cylindrical base 105). In addition, a plurality (3
The source gas supply means 106) are arranged at equal intervals on the same circumference (concentric with the arrangement circle of the cylindrical base 105).

The cylindrical base 105 is held by a rotating shaft 108, and when a motor 109 is driven, a reduction gear 110
, The rotating shaft 108 rotates, and the cylindrical base 105 is configured to rotate around its central axis in the generatrix direction. Further, the cylindrical substrate 105 can be heated by the heating element 107 disposed inside the cylindrical substrate 105.

As the high-frequency power introducing means 102, a plurality (four) of first electrodes 102A are arranged at equal intervals on the same circumference, outside the circle where the cylindrical base 105 is arranged, and further within the arrangement circle. One second electrode 102B is arranged (center position)
Have been. The high-frequency power output from the high-frequency power supplies 103A and 103B is output to the matching boxes 104A and 104A.
4B, the first electrode 102A and the second electrode 102
From B, it is supplied into the reaction vessel 101 which becomes a film formation space.

The shape of the high-frequency power introducing means 102 is not particularly limited. A rod-shaped, cylindrical, spherical, or plate-shaped cathode electrode, or a means for providing an opening in the outer conductor of the coaxial structure and supplying power therefrom can be used. From the viewpoint of preventing the film from peeling off from the high-frequency power introducing means 102, it is preferable that the film be formed as curved as possible, and it is particularly preferable that the film be cylindrical. The supply of high-frequency power to the high-frequency power introducing means 102 may be performed at one point of the high-frequency power introducing means 102 or may be performed at a plurality of points.

The surface of the high-frequency power introducing means 102 is desirably roughened for the purpose of improving the adhesion of the film, preventing peeling of the film, and suppressing dust during film formation. The specific degree of the surface roughening is preferably in the range of 5 μm to 200 μm in terms of 10-point average roughness (Rz) based on 2.5 mm.

Further, from the viewpoint of improving the adhesion of the film, it is effective that the surface of the high frequency power introducing means 102 is coated with a ceramic material. The specific means of coating is not particularly limited, but the surface of the high-frequency power introducing means 102 may be coated by a surface coating method such as a CVD method or thermal spraying. Among the coating methods, thermal spraying is preferable because it is difficult to limit the size and shape of the object to be coated from the viewpoint of cost or the coating object. Specific examples of the ceramic material include alumina, titanium dioxide, aluminum nitride, boron nitride, zircon, cordierite, zircon-cordierite, silicon oxide, and beryllium mica ceramics. The thickness of the ceramic material covering the surface of the high-frequency power introducing means 102 is not particularly limited, but is 1 μm to 10 mm in order to increase durability and uniformity, and from the viewpoint of high-frequency power absorption and manufacturing cost.
Is preferably 10 μm to 5 mm.

Further, by providing the heating or cooling means in the high-frequency power introducing means 102, the adhesion of the film on the surface thereof can be further improved, and the prevention of film peeling can be achieved more effectively. In this case, whether to heat or cool the high-frequency power supply means 102 may be appropriately determined according to the film material to be deposited and the deposition conditions.

The specific heating means is not particularly limited as long as it is a heating element. Specifically, a winding heater of a sheath-shaped heater, a plate-shaped heater, an electric resistance heating element such as a ceramic heater, a heat radiation lamp heating element such as a halogen lamp and an infrared lamp, a heat exchange means using a liquid, a gas or the like as a medium. A heating element; The specific cooling means is not particularly limited as long as it is a heat absorber. For example, a cooling coil, a cooling plate, a cooling cylinder, or the like that can flow a liquid or a gas as a cooling medium can be used.

The cylindrical substrate 105 may be either conductive or electrically insulating. As the conductive substrate, Al,
Cr, Mo, Au, In, Nb, Te, V, Ti, P
Examples include metals such as t, Pd, and Fe, and alloys thereof, for example, stainless steel. Further, a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, or the like, or at least a surface of an electrically insulating support such as glass or ceramic on which a light receiving layer is formed. Can also be used.

The surface of the cylindrical substrate 105 may be smooth or a desired uneven surface. The thickness of the cylindrical shape may be appropriately determined so that a desired product (photoconductor for electrophotography or the like) is obtained. For example, when flexibility is required for an electrophotographic photoreceptor, it can be made as thin as possible within a range where the function as a substrate can be sufficiently exhibited. However, it is usually 10 μm or more from the viewpoint of production, handling, mechanical strength and the like.

In particular, when image recording is performed using coherent light such as laser light, the cylindrical substrate 105 is formed in order to more effectively eliminate image defects caused by so-called interference fringe patterns appearing in a visible image. Irregularities may be provided on the surface. The irregularities are described in, for example, JP-A-60-168156, JP-A-60-178457, and JP-A-60-2258.
It is prepared by a known method described in JP-A-54-54 and the like.

As another method for more effectively eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, the resolution required for an electrophotographic photoreceptor on the surface of a substrate is described. There is a method in which finer irregularities are provided by a plurality of spherical trace depressions. The irregularities due to the spherical trace dents are produced, for example, by a known method described in JP-A-61-231561.

The number of the cylindrical substrates 105 arranged on the same circumference is not particularly limited. In general, as the number of cylindrical substrates is increased, the size of the apparatus is increased and the required high-frequency power supply capacity is increased. Therefore, it may be determined appropriately in consideration of these points.

The number and location of the raw material gas supply means 106 are not particularly limited. However, as described above, it is effective to install the raw material gas supply means both inside and outside the cylindrical substrate arrangement circle.

The shape of the reaction vessel 105 is not particularly limited, but it is preferable that the film formation space in which the source gas is decomposed is limited to a cylindrical region. in this case,
The reaction vessel 105 does not necessarily have to be cylindrical, and for example, a cylindrical film-forming space wall may be provided in a square reaction vessel. When restricting the film-forming space to a cylindrical region, it is preferable that the central axis of the cylindrical film-forming space passes through the center of the arrangement circle of the cylindrical substrate. It is effective to perform surface roughening, coating with ceramics, and heating / cooling on the surface of the film formation space wall in order to prevent film peeling, similarly to the surface of the high-frequency power introducing means.

The formation of a deposited film using the apparatus shown in FIG. 1 is performed, for example, as follows.

First, the cylindrical substrate 105 held by the substrate holder is set in the inside of the reaction vessel 101, and the inside of the reaction vessel 101 is evacuated through the exhaust port 111 by an exhaust device (not shown). Subsequently, the heating element 107 heats and controls the cylindrical base 105 to a predetermined temperature. When the temperature of the cylindrical substrate 105 reaches a predetermined temperature, the source gas is introduced into the reaction vessel 101 via the source gas supply means 106.

The flow rate of the raw material gas becomes the set flow rate.
After confirming that the pressure in the reaction vessel 101 has stabilized, predetermined high-frequency power is supplied from the high-frequency power supply 103 to the high-frequency introducing means (cathode electrode) 102 via the matching box 104. Glow discharge is generated in the reaction vessel by the supplied high frequency power, and the source gas is excited and dissociated to form a deposited film on the cylindrical substrate 105.

After the desired film thickness is formed, the supply of the high-frequency power is stopped, the supply of the source gas is stopped, and the formation of the deposited film is completed. When forming a deposited film having a multilayer structure, the same operation may be repeated a plurality of times. in this case,
As described above, once the formation of one layer is completed, the discharge is completely stopped between the layers, and after the setting of the gas flow rate and the pressure of the next layer is changed, the discharge is caused again to generate the next layer. May be formed, or a plurality of layers may be formed continuously by gradually changing the gas flow rate, pressure, and high-frequency power to set values of the next layer within a certain period of time after the formation of one layer. Is also good. Further, during the formation of the deposited film, the cylindrical substrate 105 may be
At 09, it is rotated at a predetermined speed.

In the apparatus shown in FIG.
A plurality of high-frequency power introduction means 102 are provided for the purpose of suppressing the difference in deposited film characteristics between the first electrode 102 and the first electrode 102.
A is arranged at equal intervals on a concentric circle having the same center as the arrangement circle of the cylindrical substrates 105.

The supply of power to the plurality of high-frequency power introducing means 102 can be performed, for example, by branching the power supply path from one high-frequency power supply via a matching box. Also, for example, after a power supply path is branched from one high-frequency power supply, power may be supplied via a plurality of matching boxes. For example, a separate high-frequency power supply and a matching box may be provided for each high-frequency power introduction unit. May be provided. However, the point that the frequency of the high-frequency power introduced from all the high-frequency power introduction means completely matches,
From the viewpoint of the cost of the apparatus and the size of the apparatus, it is preferable to supply power from one high-frequency power supply to all high-frequency power introducing means.

More specifically, high-frequency power is supplied to the first electrode 102A and the second electrode 102B from the high-frequency power source 103 via the matching box 104,
It is also possible to branch the power supply path and supply power to the first electrode 102A and the second electrode 102B. However, from the viewpoint of controllability, it is preferable that power can be independently controlled by means such as using two independent high-frequency power sources 103A and 103B and matching boxes 104A and 104B as shown in FIG.

In this case, as shown in FIG. 7 described later, the first
Oscillating source 71 of high-frequency power introduced from electrode 702A
3 and the second electrode 70 installed in the arrangement circle of the cylindrical substrate
It is further preferable that the oscillation source 713 of the high-frequency power introduced from 2B is the same.

In the apparatus shown in FIG. 1, two independent high-frequency power controls are required. This high-frequency power introduction procedure is performed after setting the power introduced from the first electrode 102A to a predetermined value. , The power introduced from the second electrode 102B may be set to a predetermined value, or the reverse procedure may be used. Further, the power supplied from the first electrode 102A and the power supplied from the second electrode 102B may be simultaneously set to a predetermined value.

Next, some embodiments of the deposited film forming apparatus of the present invention will be described with reference to the drawings. 4A and 4B are schematic views showing a further embodiment, in which FIG. 4A is a schematic cross-sectional view, and FIG. 4B is a schematic cross-sectional view along a cutting line AA ′ in FIG. In the deposited film forming apparatus shown in FIG. 4, the raw material gas introducing means 406 is installed only within the arrangement circle of the cylindrical substrate 405, and is not installed outside the arrangement circle. In the present invention, such a configuration is also possible. Also, the respective units 401 to 411 in FIG.
111.

FIGS. 6A and 6B are schematic views showing a further embodiment of the deposited film forming apparatus of the present invention. FIG. 6A is a schematic sectional view, and FIG. 6B is a sectional view taken along line AA ′ of FIG. It is an outline sectional view. The deposition film forming apparatus shown in FIG. 6 further includes a cylindrical wall member 612 at least partially made of a non-conductive material and arranged so as to surround the plurality of cylindrical substrates 605.
The central axis of the cylindrical wall member 612 passes through the center of the circle on which the cylindrical substrate 605 is arranged. Further, the plurality of first electrodes 602A arranged outside the arrangement circle of the cylindrical substrate 612 are:
It is located outside the cylindrical wall member 612, and a plurality of (3
Are provided in the cylindrical wall member 612 and inside the circle in which the cylindrical base 605 is arranged. In addition, each of the units 601 to 611 in FIG.
This corresponds to each of the units 101 to 111 in FIG.

The cylindrical wall member 612 limits the film forming space where the source gas is decomposed to a cylindrical region. The restricted area (film formation space) is such that its central axis is
Is a columnar area that passes through the center of the arrangement circle. According to the apparatus having the configuration shown in FIG. 6, the utilization efficiency of the source gas is improved, and at the same time, defects in the formed deposited film can be suppressed.

As the non-conductive material constituting at least a part of the cylindrical wall member 612, alumina, titanium dioxide,
Examples include aluminum nitride, boron nitride, zircon, cordierite, zircon-cordierite, silicon oxide, and beryllium oxide mica-based ceramics. Of these, alumina is particularly preferred because it absorbs less high frequency power.

It is also preferable to provide a cylindrical member which is maintained at a constant potential and functions as a conductive shield so as to surround a cylindrical wall member at least partially made of a non-conductive material. The central axis of the cylindrical member may be disposed so as to pass through the center of the arrangement circle of the cylindrical substrate. Furthermore, the first
It is preferable to provide the electrode 602A so as to surround the electrode 602A in order to improve the uniformity of the emitted high-frequency power. The cylindrical conductive shield may be configured to also serve as the reaction vessel 601.

FIGS. 7A and 7B are schematic views showing a further embodiment of the deposited film forming apparatus of the present invention, wherein FIG. 7A is a schematic sectional view, and FIG. 7B is a sectional view taken along the line AA ′ of FIG. It is an outline sectional view. In the deposited film forming apparatus shown in FIG. 7, the first electrode 702B, the cylindrical base 705, and the source gas introducing means 706, which are high-frequency power introducing means, are further provided than the apparatus shown in FIG.
, And one high-frequency oscillator 713 is connected to the high-frequency power supplies 703A and 703B. Also, the respective units 701 to 711 in FIG. 7 correspond to the respective units 101 in FIG.
~ 111.

The deposited film forming apparatus and the deposited film forming method according to the present invention are, for example, as shown in FIGS. 8 (a) to 8 (c).
It is very useful for the production of i-type electrophotographic photoreceptors.

In the electrophotographic photosensitive member shown in FIG. 8A, a photoconductive layer 802 made of a-Si: H, X and having photoconductivity is provided on a base 801. The electrophotographic photoconductor shown in FIG. 8B has a substrate 801 on which a-Si: H,
It is composed of a photoconductive layer 802 made of X and having photoconductivity, and an amorphous silicon-based surface layer 803.
The photoconductor for electrophotography shown in FIG. 8C has a photoconductive layer 802 made of a-Si: H, X and having photoconductivity, an amorphous silicon-based surface layer 803, and a base 801.
And an amorphous silicon charge injection blocking layer 804.

[0082]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.

<Embodiment 1> Mirror-finished Al having a length of 358 mm and an outer diameter of 80 mm was obtained using the apparatus shown in FIG.
High frequency power supply 1 on a cylinder (cylindrical substrate 105)
An electrophotographic photosensitive member was manufactured under the conditions shown in Table 1 with the oscillation frequency of No. 03 being 105 MHz.

In this embodiment, as shown in FIG. 1, six cylindrical substrates 105 are arranged on the same circumference, and the shortest distance dmm between adjacent cylindrical substrates 105 is changed as shown in Table 2. Was.

Further, as the high frequency power introducing means 102,
A stainless rod-shaped electrode having an outer diameter of 20 mm was used, and the outside thereof was covered with an alumina pipe having an inner diameter of 21 mm and an outer diameter of 24 mm. Alumina pipe has a surface roughness of 2.5 mm as a reference length by blasting.
To 20 μm. This high frequency power introduction means 102
As shown in FIG. 1, one second electrode 102B is provided at the center of the circle in which the cylindrical base 105 is arranged, and the first electrode 102A
As an example, six are arranged at equal intervals on the same circumference having the same center as the arrangement circle outside the arrangement circle of the cylindrical base 105.

The source gas supply means 106 has an inner diameter of 10 m,
An alumina pipe having an outer diameter of 13 m was used, which had a structure in which the end was sealed, and had a structure in which a raw material gas could be supplied from a gas jet port having a diameter of 1.2 mm provided on the pipe. Such source gas supply means 106 was installed inside and outside the arrangement circle of the cylindrical substrate 105. Three source gas supply means 106 in the arrangement circle are arranged at equal intervals on the same circumference having the same center as the arrangement circle of the cylindrical substrate 105. The source gas supply means 106 outside the circle where the cylindrical substrate 105 is arranged
Were arranged at equal intervals on the same circumference having the same center as the arrangement circle of the cylindrical substrate 105.

The characteristics of the electrophotographic photoreceptor thus manufactured were evaluated as follows using a Canon-made copying machine NP6750 modified for this test.
Table 2 shows the results.

"Number of spherical projections" The entire surface of the electrophotographic photosensitive member was observed with an optical microscope, and the number of spherical projections having a diameter of 15 μm or more within an area of 10 cm ² was examined and evaluated based on the number. Therefore, the smaller the numerical value, the better.

"Image defect (white spots)" A full black chart made by Canon (part number FY9-9073) is placed on a platen, and a diameter of 0.2 mm or more within the same area of a copied image obtained when copying is performed. The number of white spots (white spots) was counted and evaluated by the number. Therefore, the smaller the numerical value, the better.

[0090]

[Table 1]

[0091]

[Table 2]

In Table 2, a relative comparison is made with a value of 100 when the shortest distance d between the adjacent cylindrical substrates is d = 5 mm being produced. As is clear from the results shown in Table 2, the shortest distance dmm between the adjacent cylindrical substrates 105 was A / A.
When 3 ≦ d is satisfied, that is, the shortest distance dmm is 80
When / 3 = about 26.7, the number of spherical projections and image defects (white spots) can be significantly reduced.

<Embodiment 2> In Embodiment 1, the outer diameter φ1
An electrophotographic photoreceptor was produced in the same manner as in Example 1, except that an 08 mm (the same size of other portions) Al cylinder was used as the cylindrical substrate 105. The characteristics were similarly evaluated using a Canon copier NP6062 modified for this test. Table 3 shows the results.

[0094]

[Table 3]

In Table 3, a relative comparison is made with a value of 100 when the shortest distance d between the adjacent cylindrical substrates is d = 5 mm as 100. As is clear from the results shown in Table 3, the shortest distance dmm between the adjacent cylindrical substrates 105 was A / A.
When 3 ≦ d is satisfied, that is, the shortest distance dmm is 10
When it is larger than 8/3 = 36, it can be seen that the number of spherical projections and image defects (white spots) are significantly reduced.

<Embodiment 3> The shortest distance d between the adjacent cylindrical substrates 105 was fixed at 40 mm, the diameter L of the arrangement circle of the cylindrical substrates was fixed at 240 mm, and the frequency of the high frequency power supply was changed as shown in Table 4. Except for this, an electrophotographic photoconductor was produced in the same manner as in Example 1.

Regarding the characteristics of the electrophotographic photoreceptor, the Canon copying machine NP6750 modified for this test was used.
Was evaluated as follows. Table 4 shows the obtained results.
Shown in

[Charging Ability] The surface potential of the dark portion at the developing device position when a constant current was passed through the main charger of the copying machine was measured with a surface voltmeter, and the value at this time was defined as the charging ability. Therefore, the larger the dark area potential, the better the charging ability. The measurement of the charging ability was performed over the entire area of the photoconductor bus direction, and the evaluation was made based on the lowest dark area potential.

[Ghost memory] After adjusting the current value of the main charger so that the dark portion potential at the developing device position becomes a predetermined value, the dark portion potential when a predetermined white paper is used as an original document becomes the predetermined value. The image exposure light amount was adjusted, and in this state, a ghost test chart made by Canon (part number: FY9-90)
When a black circle having a reflection density of 1.1 and a diameter of φ5 mm is pasted on 40) and placed on the leading edge of the image on the platen, and a Canon halftone chart (part number: FY9-9042) is placed on top of it. Of the ghost chart observed on the halftone copy, the difference between the reflection density of the black circle having a diameter of φ5 mm and the reflection density of the halftone portion was measured. Therefore, the smaller the numerical value, the better. The ghost memory measurement was carried out over the entire area of the photoconductor in the generatrix direction, and was evaluated based on the maximum reflection density difference.

[Characteristic variation] For two items, charging ability and ghost memory, the maximum and minimum values of the evaluation results of all the photoconductors in each evaluation were obtained, and then (maximum value) /
(Minimum value) was determined. Of the two items, the one with the largest value was taken as the value of the characteristic variation. Therefore, the smaller the numerical value, the better.

[0101]

[Table 4]

In Table 4, the frequency is 13.56 MHz.
Relative comparison was performed with the value at the time of the production of 100 as 100.
As is clear from the results shown in Table 4, the frequencies 50 to 45
It can be seen that good results are obtained within the range of 0 MHz.

<Embodiment 4> The oscillation of the high frequency power supply 403 was performed on an Al cylinder (cylindrical substrate 405) having a length of 358 mm and an outer diameter of φ80 mm, which was mirror-finished, using the deposited film forming apparatus shown in FIG. An electrophotographic photoreceptor was manufactured under the conditions shown in Table 5 at a frequency of 105 MHz.

In this embodiment, θ shown in FIG.
(The first electrode 502A is on a line connecting the second electrode 502B and the center of the cylindrical substrate 505) to 30 ° (the first electrode 502A is disposed between the cylindrical substrates 505, and the second electrode 502B A straight line connecting the first electrode 502A and the first electrode 502A passes through the center between the adjacent cylindrical substrates 505).

As shown in FIGS. 4 and 5, six cylindrical substrates 405 are formed on the same circumference, and adjacent cylindrical substrates 405 are formed.
5 was set so that the shortest distance d was 40 mm, and the diameter L of the arrangement circle of the cylindrical base 405 was 240 m.

The high-frequency power supply means 402 and the source gas supply means 406 used were the same as in the first embodiment.

<Comparative Example 1> An electrophotographic photoreceptor was manufactured under the conditions shown in Table 5 in the same manner as in Example 4 using the deposited film forming apparatus shown in FIG. In this comparative example, the power is only the second electrode 202. The second electrode 202 is the same as that of the fourth embodiment.
The same high-frequency power supply means 402 as shown in FIG. 2 was used, and as shown in FIG. The same material gas supply means 206 as the material gas supply means 406 of Example 4 was used, and three material gas supply means 206 were similarly arranged at equal intervals.

In this comparative example, the cylindrical substrate 205
A with mirror length of 358mm and outer diameter φ80mm
and the shortest distance d between adjacent cylindrical substrates 205
Is 5 mm, and the diameter L of the arrangement circle of the cylindrical substrate 205 is 222
mm.

The charging ability and ghost memory of the electrophotographic photosensitive members obtained in Example 4 and Comparative Example 1 were evaluated in the same manner as described above, using a Canon copying machine NP6750 modified for this test. Table 6 shows the obtained results.

[0110]

[Table 5]

[0111]

[Table 6]

In Table 6, the value in Comparative Example 1 was 100
And a relative comparison was performed. As is clear from the results shown in Table 6, in Example 4, good results were obtained. Further, a first electrode 402A arranged outside the circular arrangement of the cylindrical base 405 is arranged between the cylindrical bases, and a straight line connecting the second electrode 402B and the first electrode 402A is connected to the adjacent cylindrical base 405. It was found that the charging ability and the characteristics of the ghost memory were greatly improved by arranging them so as to pass through the center between them.

<Embodiment 5> Using the deposited film forming apparatus shown in FIG. 6, an oscillation of a high-frequency power source 603 was performed on a mirror-finished Al cylinder (cylindrical base 605) having a length of 358 mm and an outer diameter of 80 m. An electrophotographic photoreceptor was manufactured under the conditions shown in Table 7 at a frequency of 105 MHz.

In this embodiment, the film forming space in which the source gas is decomposed is formed by the cylindrical wall material 612 and the cylindrical substrate 6.
05 is limited to a cylindrical region. The cylindrical wall surface 612 has an inner diameter of 400 mm, a thickness of 20 m, and a height of 500 m.
m made of an alumina cylinder. Cylindrical wall material 612
The inner surface has a surface roughness of 2.5 mm by blasting.
Was set to 20 μm in Rz with reference to.

As shown in FIG. 6, the number of the cylindrical substrates 605 is six on the same circumference, the shortest distance d between the adjacent cylindrical substrates 605 is 50 mm, and the diameter L of the circle in which the cylindrical substrates 605 are arranged.
Was set to 260 mm.

The high frequency power introducing means 602 has a length of 470
A stainless steel rod-shaped electrode having an outer diameter of φ20 mm was used. The installation position is set outside the cylindrical wall member 612 made of non-conductive material made of alumina, and the first electrode 6 is placed on the same circumference.
Six straight lines connecting the second electrode 02A and the second electrode 602B pass through the center between the adjacent cylindrical substrates 605, and are arranged at an interval of 30 mm from the outer surface of the cylindrical wall member 612. The second electrode 602B has a structure in which a stainless rod-shaped electrode having a diameter of 20 mm and a length of 470 mm is used, and the outside thereof is covered with an alumina pipe having an inner diameter of 21 mm and an outer diameter of 24 mm. It was installed in the center of the inside. Alumina pipe is blasted,
The surface roughness was set to 20 μm in Rz with 2.5 m as a reference length.

The reaction vessel 601 is an aluminum cylindrical vessel, and also serves as a shielding means for a high-frequency power introducing means provided outside the cylindrical wall member 612.

The structure of the raw material gas supply means 606 is the same as that of the fourth embodiment, and the installation positions are set inside and outside the cylindrical substrate arrangement circle. The three source gas supply means 606 in the cylindrical substrate arrangement circle are arranged at equal intervals on the same circumference having the same center as the cylindrical substrate arrangement circle. The raw material gas supply means 606 outside the circular arrangement of the cylindrical substrate is
6 at equal intervals on the same circumference with the same center as the arrangement circle of 5
This book was arranged.

The electrophotographic photoreceptor manufactured in this manner is replaced with a Canon copier NP modified for this text.
-6750, and the characteristics of the photoreceptor were evaluated. The evaluation items were “image defect” similar to the previous example, “image density unevenness” and “characteristic variation (chargeability, ghost memory, image density unevenness)” described below. Table 8 shows the results.

"Image density unevenness" First, after adjusting the main charger current so that the dark portion potential at the developing device position becomes a constant value,
A predetermined white paper having a reflection density of 0.1 or less was used as an original, and the amount of image exposure light was adjusted so that the bright portion potential at the developing device position became a predetermined value. Then, the Canon halftone chart (part number:
FY9-9042) was placed on a platen and evaluated by the difference between the highest value and the lowest value of the reflection density in the entire area of the copy image obtained when copying. The evaluation results were average values of all the photoconductors. Therefore, the smaller the numerical value, the better.

"Characteristic variation" In the three items of the charging ability and the ghost memory evaluated in the same manner as in the previous embodiment, and the image density unevenness described above, the maximum value and the minimum value of the evaluation results of all the photosensitive members in each evaluation. , Then (maximum)
/ (Minimum value) was determined. Of the three items, the one with the largest value was taken as the value of the characteristic variation. Therefore, the smaller the numerical value, the better.

Further, in these evaluation results (Table 8), the result of Example 4 was used as a reference,
% Or more, “◎”, 30% or more and less than 40%, and “○”, 20% or more and less than 30%.
The improvement of 0% or more and less than 20% was indicated by “○”, the improvement of less than 10% was indicated by “Δ”, and the deterioration was indicated by “X”.

[0123]

[Table 7]

[0124]

[Table 8]

As is evident from the results shown in Table 8, better results were obtained with respect to "image defects" than in Example 4, and "Image Defects" and "Characteristic Variation" were the same as those in Example 1. Equivalent good results were obtained. For this reason, the high-frequency power introducing means 602A is connected to the cylindrical wall member 612.
It can be seen that a significant effect in suppressing image defects can be obtained by adopting a configuration that is installed outside the above.

<Embodiment 6> Using a deposition film forming apparatus shown in FIG. 7, on a mirror-finished Al cylinder (cylindrical substrate 705) having a length of 358 mm and an outer diameter of φ30 mm under the conditions shown in Table 9, An electrophotographic photoreceptor was prepared.

In this embodiment, the high-frequency power is such that the signal output from the high-frequency oscillator 713 is divided into two systems, amplified by the amplifiers 703A and 703B, and supplied to the matching boxes 704A and 704B. . High frequency oscillation 7
The frequency of No. 13 was 105 MHz.

The film forming space in which the source gas is decomposed is the same as that of the fifth embodiment, and the cylindrical wall
It is limited to the enclosing cylindrical region. Cylindrical substrate 70
5 has an inner diameter of 250 mm, a thickness of 15 m, and a height of 50
The inner surface was made of 0 mm alumina, and the inner surface was blasted to have a surface roughness of 20 μm in Rz with a reference length of 2.5 mm.

The cylindrical substrate 705 has 12
Book, the minimum distance d between adjacent cylindrical substrates 705 is 10 m
m, the diameter L of the circle on which the cylindrical substrate 705 was arranged was set to 156 mm.

The structure of the high frequency power introducing means 702 is the same as that of the high frequency power introducing means 502 of the fifth embodiment. In addition, twelve first electrodes 702A were placed outside the cylindrical substrate arrangement circle, and were placed at an interval of 25 m from the cylindrical wall surface 412. One second electrode 702B was provided at the center of the circle on which the cylindrical substrate was arranged. The reaction vessel 701 and the raw material gas supply means 706 are the same as in the fifth embodiment.

The electrophotographic photoreceptor manufactured in this manner is changed to a Canon copier NP modified for this text.
6030, and the characteristics of the photoreceptor were evaluated. The evaluation items were the same three items as described above: “image defect image”, “image density unevenness”, and “characteristic variation”, and each item was evaluated. Table 10 shows the evaluation results. Further, in these evaluation results (Table 10), as in the evaluation of Example 5 (Table 8), the results of Example 4 were used as a reference and compared with the results.

[0132]

[Table 9]

[0133]

[Table 10]

As is evident from the results shown in Table 10, better results were obtained with respect to image defects and characteristic variations as compared with Example 4, and good results similar to Example 4 were obtained with respect to image density unevenness. Obtained.

[0135]

As described above, according to the present invention,
In the formation of a deposited film by a high-frequency plasma CVD method, structural defects and variations in film characteristics are suppressed, and a deposited film having excellent characteristics can be uniformly formed over a large area.

Therefore, according to the present invention, for example, it is possible to stably produce semiconductor devices, electrophotographic photoreceptors, and the like having excellent characteristics at low cost, which is very useful in such fields. .

[Brief description of the drawings]

FIG. 1 is a schematic view showing an embodiment of a deposited film forming apparatus according to the present invention, in which (a) is a schematic sectional view and (b) is (a).
FIG. 4 is a schematic sectional view taken along a cutting line AA ′ of FIG.

FIGS. 2A and 2B are schematic views showing an example of a conventional deposited film forming apparatus, in which FIG. 2A is a schematic sectional view, and FIG. 2B is a schematic sectional view along a cutting line AA ′ in FIG.

FIG. 3 is a view showing the result of observing the number of spherical protrusions on the surface of a substrate on which a deposited film is formed using a conventional deposited film forming apparatus, and (a) is a schematic cross section showing the positional relationship between an electrode and a cylindrical substrate FIG. 3B is a graph showing the correlation between the spherical projection ratio and the circumferential angle.

FIG. 4 is a schematic view showing a further embodiment of a deposited film forming apparatus according to the present invention, wherein (a) is a schematic sectional view thereof, and (b).
FIG. 3 is a schematic cross-sectional view taken along a cutting line AA ′ of FIG.

FIG. 5 is a schematic diagram showing conditions of a fifth embodiment.

FIG. 6 is a schematic view showing a further embodiment of the deposited film forming apparatus of the present invention, wherein (a) is a schematic sectional view thereof, and (b).
FIG. 3 is a schematic cross-sectional view taken along a cutting line AA ′ of FIG.

FIGS. 7A and 7B are schematic views showing a further embodiment of the deposited film forming apparatus of the present invention, wherein FIG. 7A is a schematic sectional view thereof, and FIG.
FIG. 3 is a schematic cross-sectional view taken along a cutting line AA ′ of FIG.

FIGS. 8A to 8C are schematic diagrams each showing an a-Si-based electrophotographic photoconductor that can be suitably manufactured according to the present invention.

[Explanation of symbols]

101, 201, 401, 601, 701 Reaction vessels 102A, 302A, 402A, 502A, 602A,
702A First electrode (high-frequency power introducing means) 102B, 402B, 502B, 602B, 702B
Second electrode (high-frequency power introducing means) 103A, B, 203, 403A, B, 603A, B, 7
03A, B High frequency power supply 104A, B, 204,404A, B, 604A, B, 7
04A, B Matching box 105, 205, 305, 405, 505, 605, 7
05, 801 Cylindrical substrate 106, 206, 406, 606, 706 Source gas introducing means 107, 207, 407, 607, 707 Heating element 108, 208, 408, 608, 708 Rotation axis 109, 209, 409, 609, 709 Motor 110, 210, 410, 610, 710 Reduction gear 111, 211, 411, 611, 711, exhaust port 202 High frequency power introduction means 612, 712 Cylindrical wall material 703 Amplifier 713 High frequency oscillator 802 Photoconductive layer 803 Surface layer 804 Charge Injection blocking layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/31 H01L 21/31 C (72) Inventor Kazutaka Akiyama 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Takashi Otsuka 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Daisuke 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Hitoshi Murayama 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Tatsuyuki 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (Reference) 2H068 DA23 EA25 EA30 EA36 4K030 AA05 AA06 BA30 CA02 CA16 FA03 JA03 JA18 KA05 LA17 5F045 AA08 AB04 AC01 AC07 AC14 AD06 AD07 AD08 AE11 AE13 AE15 AE17 AE19 AE21 AF10 BB14 BB16 CA16 DP25 EC05 EF03 EH06 EH10 EK07 EK09 EK10 EK11 EM10

Claims (20)

[Claims] 1. A vacuum-tightly sealed reaction vessel having a plurality of mounting portions for supporting a cylindrical substrate, a source gas supplied into the reaction vessel is decomposed, and a deposited film is formed on the cylindrical substrate. In the deposited film forming apparatus to be formed, when the diameter of the cylindrical substrate is Amm, the shortest distance dmm between adjacent cylindrical substrates satisfies A / 3 ≦ d,
And the diameter Lmm of the circle of arrangement of the cylindrical substrate is 2000 ≧ L
Wherein the plurality of mounting portions are arranged at equal intervals on the same circumference, and a plurality of high-frequency power introducing means are arranged outside the arrangement circle of the mounting portions. Deposition film forming equipment. 2. The high-frequency power introducing means has a frequency of 50 to 50.
2. The deposition film forming apparatus according to claim 1, wherein the means is capable of introducing high-frequency power of 450 MHz. 3. The deposition film forming apparatus according to claim 1, wherein a plurality of high-frequency power introducing means are arranged at equal intervals on the same circumference having the same center as the arrangement circle of the mounting portion. 4. A plurality of high-frequency power introducing means (first electrodes) disposed outside the placement circle of the mounting portion, and high-frequency power introducing means (second electrodes) disposed within the placement circle. The deposited film forming apparatus according to any one of claims 1 to 3, further comprising: 5. A straight line connecting the first electrode and the second electrode,
5. The deposited film forming apparatus according to claim 4, wherein the deposited film forming apparatus is disposed so as to pass through the center between the adjacent mounting portions. 6. The deposited film forming apparatus according to claim 4, wherein the high-frequency power introduced from the first electrode and the high-frequency power introduced from the second electrode can be independently controlled. 7. The first electrode and the second electrode from one oscillation source.
7. The deposited film forming apparatus according to claim 6, wherein high-frequency power is introduced to said electrode. 8. The apparatus according to claim 8, further comprising a cylindrical wall member at least partially made of a non-conductive material, which is disposed so as to surround the plurality of mounting portions, wherein a center axis of the cylindrical wall material is set to a position of the mounting portion. The plurality of high-frequency power introducing means arranged through the center of the arrangement circle and outside the arrangement circle of the mounting portion are located outside the cylindrical wall material. Deposition film forming equipment. 9. A cylindrical member which is maintained at a constant potential and functions as a conductive shield is provided so as to surround a cylindrical wall member at least partially made of a non-conductive material, and a central axis of the cylindrical member is provided. 9. The deposition film forming apparatus according to claim 8, wherein the device is disposed so as to pass through the center of the placement circle of the mounting portion. 10. The deposited film forming apparatus according to claim 1, wherein the raw material gas supply means is disposed inside and outside the arrangement circle of the mounting portion. 11. A cylindrical substrate is supported on a plurality of mounting portions in a vacuum-tight reaction vessel, and a raw material gas supplied into the reaction vessel is decomposed to form a deposited film on the cylindrical substrate. In the method for forming a deposited film, a plurality of the cylindrical substrates are arranged at equal intervals on the same circumference,
A plurality of high-frequency power introducing means are arranged outside the circle of the cylindrical base, and when the diameter of the cylindrical base is A mm, the shortest distance dmm between adjacent cylindrical bases is A / 3 ≦ d. And the diameter Lmm of the arrangement circle of the cylindrical substrate is 20
A method for forming a deposited film, wherein the deposited film is formed in an arrangement satisfying 00 ≧ L. 12. The high frequency power introduced by the high frequency power introduction means has a frequency of 50 to 450 MHz.
2. The method for forming a deposited film according to claim 1. 13. The deposition film forming method according to claim 11, wherein a plurality of high-frequency power introducing means are arranged at equal intervals on the same circumference having the same center as the arrangement circle of the cylindrical substrate. 14. A plurality of high-frequency power introducing means (first electrodes) arranged outside the circle on which the cylindrical substrate is arranged, and high-frequency power introducing means (second electrodes) arranged within the circle. The method for forming a deposited film according to any one of claims 11 to 13, wherein an apparatus having: 15. The method according to claim 14, wherein a straight line connecting the first electrode and the second electrode is disposed so as to pass through a center between adjacent cylindrical substrates. 16. The method according to claim 14, wherein the high-frequency power introduced from the first electrode and the high-frequency power introduced from the second electrode can be independently controlled. 17. The method according to claim 16, wherein high-frequency power is introduced from one oscillation source to the first electrode and the second electrode. 18. An apparatus further comprising a cylindrical wall member at least partially made of a non-conductive material disposed so as to surround a plurality of cylindrical substrates, wherein a central axis of the cylindrical wall member is the cylindrical axis. 18. A plurality of high-frequency power introducing means passing through the center of the arrangement circle of the base and outside the arrangement circle of the cylindrical base are located outside the cylindrical wall material. The method for forming a deposited film according to the above. 19. A cylindrical member which is maintained at a constant potential and functions as a conductive shield is provided so as to surround a cylindrical wall member at least partially made of a non-conductive material, and a central axis of the cylindrical member is provided. 19. The deposited film forming method according to claim 18, wherein is disposed so as to pass through the center of the arrangement circle of the cylindrical substrate. 20. The deposited film forming method according to claim 11, wherein the source gas supply means uses an apparatus disposed inside and outside the circle where the cylindrical substrate is arranged.