JP2003089876A - Device and method for manufacturing functional deposition film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive and efficient device and/or an efficient method for obtaining a functional deposition film of high quality when forming the functional deposition film. SOLUTION: In a vapor phase deposition film manufacturing device comprising a sealable reaction chamber, a substrate holder to install a cylindrical substrate in the reaction chamber, and a deposition film forming means for performing vapor phase growth of the deposition film on the cylindrical substrate arranged on the substrate holder, the substrate holder has a substrate rotating mechanism to rotate the cylindrical substrate installed on the substrate holder around the central axis by using hydraulic power. In a deposition film manufacturing method, the vapor phase growth of the deposition film is performed while rotating the cylindrical substrate around the central axis by using the manufacturing device utilizing the hydraulic power.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and method for manufacturing an electrophotographic photosensitive member having a functional film formed thereon.

[0002]

2. Description of the Related Art There have been many applications for a method of rotating a substrate in an apparatus for forming a functionally deposited film, for example, Japanese Patent Laid-Open No.
JP-A-57-210344 and JP-A-58-33830 describe a mechanism and a method for rotating a substrate using a motor when forming a functional deposited film. And the method is not described.

Glass, heat-resistant synthetic resin, stainless steel, aluminum, etc. have been proposed as a substrate for forming a functional deposited film. Particularly in the case of a base material of an electrophotographic photoreceptor, practically, charging, exposure, development, transfer,
Metals are often used to withstand electrophotographic processes such as cleaning and to maintain high positional accuracy at all times without compromising 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.

Taking an electrophotographic photosensitive member as an example, these materials have a substrate surface-treated according to their use,
A light receiving layer is formed on the surface. The technology relating to the surface processing of the medium is disclosed in JP-A-61-231561 and JP-A-62-95.
It is described in Japanese Patent No. 545.

As a technique for element members used in electrophotographic photoreceptors, it has been proposed to use various materials such as selenium, cadmium sulfide, zinc oxide, amorphous silicon, and organic materials such as phthalocyanine. Among them, a non-single-crystal deposited film containing silicon atoms as a main component typified by amorphous silicon, for example, an amorphous silicon deposited film such as amorphous silicon compensated with hydrogen and / or halogen (eg, fluorine, chlorine) has high performance. , Has been proposed as a highly durable and pollution-free photoconductor, some of which have been put to practical use. Japanese Unexamined Patent Publication No. 54-86341 discloses a technique of an electrophotographic photoreceptor 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, there have been conventionally used a sputtering method, a method of decomposing a source gas by heat (thermal CVD method), and a method of decomposing a source gas by light (optical CVD method), a method of decomposing the 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-like deposited film on a substrate is a method for 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 advantages of 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. 518. The technology described in the patent is 0.1T.
A high-quality deposited film is obtained at a high deposition rate by a microwave plasma CVD method at a low pressure of orr or less.

Further, a technique for improving the utilization efficiency of the raw material gas by the microwave plasma CVD method is disclosed in JP-A-60-1.
No. 86849. The technique described in the publication is arranged to form an internal chamber (that is, a discharge space) by arranging a substrate so as to surround a means for introducing microwave energy, so that the raw material gas utilization efficiency is greatly enhanced. It is a thing.

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

[0011]

However, as in recent years, 1) the high image quality of the electrophotographic apparatus is required, the resolution in the development process is improved accordingly, and 2) the speed of the copying machine is increased and the charging conditions are increased. As the situation becomes severer, the part of the surface where no electric potential is applied has a large effect on the electric potential of the surroundings. It has come to be pointed out as a defect.

Further, in the past, the main purpose of copying was a manuscript with only printed characters (so-called line copy), so these image defects did not pose a serious problem in practical use. However, as the image quality of a copying machine has recently increased, many originals including halftones such as photographs have been copied, which has become a problem. In particular, in the color copiers that have recently become widespread, these defects have become more serious problems because they become more visually apparent.

Since these changes are minute, they cannot be detected even if an electrode is attached to the upper part and the conductivity is measured.
However, when the electrophotographic photosensitive member is charged, exposed, and developed by the electrophotographic process, particularly when a uniform image is formed in halftone, even a slight potential difference on the surface of the electrophotographic photosensitive member causes image defects. It may appear as a visually prominent one. In particular, in the case of the electrophotographic photoconductor prepared by the microwave plasma CVD method,
The above-mentioned problem becomes more likely to appear more prominently.

On the other hand, it is characteristic of the electrophotographic photosensitive member produced by the plasma CVD method that such an image defect appears remarkably and becomes a problem. The Se electrophotographic photosensitive member produced by vacuum vapor deposition, In the OPC electrophotographic photosensitive member prepared by the blade coating method or the dipping method, the image defects are not so remarkable as a comparison.

Also in the device produced by the plasma CVD method, the above-mentioned problem is encountered in the device such as the solar cell in which the subtle difference in the characteristics depending on the position on the substrate does not affect the performance or the device can be corrected by the post-treatment. Does not occur.

On the other hand, in terms of hardware, in order to make the deposited film uniform, in order to rotate the substrate, a method of rotating the substrate through a gear using an electric motor is adopted. Water is used for the purpose of cooling the rotating shaft itself in order to suppress such problems and obtain smooth rotation.
However, in such a configuration, investment in terms of the apparatus is also large, and durability and maintainability are further required.

The object of the present invention is to manufacture various functional deposited films, especially electrophotographic photoreceptors, which can inexpensively and efficiently obtain high-quality images in order to overcome various problems that occur during the formation of functional deposited films. A suitable apparatus and method are provided.

[0018]

That is, according to the present invention, a reaction chamber that can be sealed, a substrate holder for placing a cylindrical substrate in the reaction chamber, and a cylindrical substrate arranged in the substrate holder are deposited. In the apparatus for producing a vapor-deposited film, which comprises a deposited film forming means for vapor-depositing a film, the substrate holder has a cylindrical substrate mounted on the substrate holder whose central axis is controlled by water power. The present invention relates to an apparatus for producing a deposited film, which is characterized by having a substrate rotating mechanism for rotating it to the center.

Further, in the method for producing a deposited film by introducing a source gas into a reaction chamber in a closed state in which a cylindrical substrate is arranged to vapor-deposit the deposited film on the cylindrical substrate, The present invention relates to a method for producing a deposited film, characterized in that the deposited film is vapor-grown while the substrate is rotated about its central axis by utilizing hydraulic power.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The above-described structure of the present invention has been earnestly studied by the present inventors in order to overcome the above-mentioned problems at the time of forming a conventional deposited film and achieve the object of the present invention. Results The following examination results have resulted in completion.

For example, by mounting the substrate on the substrate holder,
When an amorphous silicon deposition film is formed on the substrate by plasma CVD on the surface of the substrate under reduced pressure, the reaction for forming the film includes the decomposition process of the source gas in the vapor phase, the discharge space to the substrate surface. It can be divided into three processes, that is, the transport process of the active species and the surface reaction process on the surface of the substrate.
In order to form a uniform deposited film on the entire surface of a large-area substrate like an electrophotographic photosensitive member in various processes, it is necessary to suppress unevenness of each reaction process on the entire substrate as much as possible.

The present inventors have focused their attention on water that has been conventionally used only for cooling the rotating mechanism and the cathode electrode,
It is considered that equipment investment can be reduced by rotating the substrate using this water and an efficient system can be provided, and the present invention has been completed by realizing a configuration for rotating the substrate holder by water power. Came to do.

In the present invention, by using water for rotating the substrate holder, it is possible to eliminate a portion where metal or non-metal has been in contact with each other in the case of using the conventional motor, and as a result, maintenance against wear and wear is performed. It has become possible to drastically reduce expenses such as expenses and electricity related to driving of motors, etc., and it has been possible to reduce costs. In addition, it was possible to suppress the knocking at the time of rotation and the subtle vibration of the rotating shaft caused by the vibration of the gear.

As a result, it is considered possible to suppress unevenness and variations in the various processes described above and obtain a more uniform and high quality functional deposited film than ever before. In particular, the cooling effect of the rotating mechanism can be enhanced, and the durability of the vacuum seal, etc. has been improved. As a result, it is possible to suppress the effect of leaks on the deposited film, and it is possible to obtain a high-quality functional deposited film. It is thought that it became.

Hereinafter, the present invention will be described by way of example when it is used in a method for manufacturing an electrophotographic photosensitive member having an aluminum alloy cylinder as a base. FIG. 1 shows an example of a deposited film forming apparatus by the plasma CVD method which can be used in the present invention. The deposited film forming by this apparatus will be described below.

The substrate was formed as follows.
First, a diamond cutting tool (trade name:
Set a miracle bite (made by Tokyo Diamond) so as to obtain a rake angle of 5 ° with respect to the center angle of the cylinder. Next, while chucking the substrate to the rotary flange of this lathe and spraying white kerosene from the attached nozzle together with suction of cutting chips with the vacuum nozzle also attached,
The outer shape is 1 under the condition of 1000m / min and feed rate 0.01mm / R.
Mirror cutting is performed so that it becomes 08 mm.

After the cutting, the substrate surface is degreased and cleaned by using a cleaning device (not shown).

Next, a deposited film mainly composed of amorphous silicon is formed on the substrate after the cutting and pretreatment by the deposited film forming apparatus by the plasma CVD method shown in FIG. In FIG. 1, a reaction vessel 101 is configured to have a base plate 104, a wall 102 also serving as a cathode electrode, and a top plate 103, which are insulated from each other by an insulator 105. This reaction vessel 101
Inside, the substrate 106 on which the amorphous silicon deposited film is formed is installed in the central portion of the cathode electrode 102 while being held by the substrate holder 117, and the substrate 106 also serves as the anode electrode.

In order to form an amorphous silicon deposited film on the substrate 106 using this deposited film forming apparatus, first, the source gas injection valve 111 is closed, and an exhaust pump (not shown) is used to react through the exhaust path 118. Container 10
Exhaust the inside of 1. Reading of vacuum gauge (not shown) is about 133 ×
When the pressure becomes 10 ⁻⁶ Pa, the raw material gas inflow valve 111 is opened.

The gas flow rate is the mass flow controller 11
Within 2, the flow rate is adjusted to a predetermined value. For example, a raw material gas such as SiH ₄ gas is passed through the raw material gas introduction pipe 109 to form a reaction container 1
01 inside.

After confirming that the surface temperature on the substrate 106 is set to a predetermined temperature by the heater 108, the high frequency power source (frequency: 13.56 MHz) 116 is set to a desired power and the inside of the reaction vessel 101 is set. Cause a glow discharge. At this time, in order to make the deposited film uniform, the substrate 1
Rotate 06. The rotation of the base body is performed by utilizing hydraulic power. That is, water required for rotation is supplied to the rotating mechanism 114 from the water conduit 115a, and the water flow causes the substrate 106 to rotate about the rotating shaft 119.

FIG. 7 shows a view of the rotating mechanism of FIG. 1 as seen from directly below.
Another mode is shown in FIG. 7 (B) and FIG. 7 (C). In the configuration represented by FIG. 7A, three or more flat blades 702 (four blades in the figure) are attached to the shaft 701 at equal angles, and the water flow force in one direction is constant. The shaft 701 can be rotated. Since the blade is a flat plate, it is advantageous in terms of cost.

FIG. 7B shows a configuration in which the blade 703 is bent, and has an advantage that the rotation direction is constant and reverse rotation is difficult. Further, in the configuration of FIG. 7C, instead of using the blade, the shaft 711 itself has a notch 712 so that the shaft 711 rotates only in one direction.

The above is the case where the outer wall of the rotating mechanism is a cylinder, but a rectangular parallelepiped is also possible. FIG. 7D corresponds to FIG. 7A and can be similarly applied to the configurations of B and C. It should be noted that the rotating mechanism in the present invention may be any mechanism as long as it can convert hydraulic power into rotational force, and is not limited to the above-mentioned respective configurations.

The bearing seals are shown in FIG.
There is a method using the configuration shown in (C). FIG. 8 (A) shows the most common O-ring seal, which is cost-effective and has sufficient performance for general applications. On the other hand, FIG.
(C) is applied when more emphasis is placed on durability,
(B) is a metal seal and (C) is a magnetic fluid seal.

The water used for rotation is the cathode electrode 102.
After being introduced into the cathode electrode 102 from the water conduit 115b at the upper end of the cathode electrode 102, the cathode electrode 102 is also cooled by passing through the cathode electrode 102 and being discharged from the drain pipe 115c at the lower end of the cathode electrode 102. In this way, the amorphous silicon deposited film can be formed on the substrate 106.

On the other hand, FIG. 2 has the same structure as the device of FIG. 1 except that the gear and motor 214 are used as a conventional rotating mechanism and the water conduit 115 is omitted (the lower two digits of the reference numerals correspond respectively). is there.

FIG. 3 shows the rotary mechanism of the present invention applied to a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a microwave plasma CVD method. In the example shown here, as shown in the XX cross-sectional view shown in FIG. 3B, six bases 306 are arranged symmetrically at intervals of 60 ° around the source gas introduction tube and the DC application electrode 308. But
The number of substrates is not limited as long as the conditions can be substantially the same.

FIG. 3A is a schematic vertical sectional view. Although the reaction vessel 301 is a substantially rectangular parallelepiped here, it may be a cylindrical shape. The exhaust pipe 304 in the lateral direction, the source gas introduction pipe in the central portion, and the waveguide 31 directly above and directly below the direct current application electrode 308.
1 extends in the vertical direction and has a circular microwave introduction window 3
Have 10. A DC power supply 309 is used to apply a DC application electrode 30.
8 is applied to the substrate 3 via the discharge space 307.
The deposited film is formed at 06. The microwave frequency at this time is 2.45 GHz.

The heater 303, rotating mechanism 302, rotating shaft 313, etc. are the same as those shown in FIG. Although only the rotating mechanism portion of the water conduit 312 is shown in this figure, it may be used for cooling by a mechanism similar to that of FIG.

On the other hand, FIG. 4 has the same structure as that of the device of FIG. 3 except that a gear and a motor 402 are used as a conventional rotating mechanism and a water conduit 312 is omitted (the lower two digits of the reference numerals correspond respectively). is there.

FIG. 5 is a schematic vertical sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by the VHF plasma CVD method. Base 506, heater 50
3, rotation mechanism 502, water conduit 509, exhaust pipe 504,
The rotating shaft 513, the discharge space 507, etc. are the same as those in FIG.

In this structure, the reaction vessel 501 lacks the DC application electrode, the DC power supply, the microwave introduction window, the waveguide, etc. as shown in FIG. 3, and instead has the VHF power supply means 505 in the central portion thereof. The lower part is connected to the VHF power source 508 just below the outside of the reaction vessel 501.

FIG. 6 is a sectional view showing the layer structure of an electrophotographic photosensitive member manufactured using the apparatus of the present invention.
In (A), reference numerals 601 and 602, 603, and 604 represent a substrate, a charge injection blocking layer, a photoconductive layer, and a surface layer, respectively. Also, in FIG. 6B, 601, 602, 60
Reference numerals 3-1 602.3-2 and 604 denote an aluminum substrate, a charge injection blocking layer, a charge transport layer, a charge generation layer and a surface layer, respectively.

In the present invention, the surface of the substrate is subjected to a surface treatment of irregularities, and is made a mirror surface or a non-mirror surface for the purpose of preventing interference fringes, or a substrate having irregularities of a desired shape is used. Is also effective.

The temperature of water in the rotating mechanism in the present invention is
It may be set according to the vapor phase growth method to be used, but if the water temperature is too low, the device may be affected by dew condensation, etc., and if it is too high, the cooling effect on the rotating shaft itself that rotates the substrate may be reduced. As it fades, the temperature is 10 ℃ or more, 60 ℃
Below, preferably 15 ℃ or more, 55 ℃ or less, optimally 2
A temperature of 0 ° C or higher and 50 ° C or lower is suitable.

In the present invention, the rotation speed when rotating the substrate is 0.5 rpm or more, 60 rpm or more in order to further improve the durability of the apparatus and the film formation efficiency and quality during deposition.
The following value is preferably 1 rpm or more and 40 rpm or less.

The shape of the substrate in the present invention is determined as desired, but if it is used for electrophotography, for example, in the case of a continuous high speed copying machine, it is an endless belt or a cylindrical shape as described above. Is most suitable for the present invention. In the case of a cylindrical shape, the size of the substrate is not particularly limited, but practically, the diameter is preferably 20 mm or more and 500 mm or less and the length is 10 mm or more and 1000 mm or less.

The thickness of the substrate is appropriately determined so that a desired functional deposited film is formed. However, when the possibility of the functional deposited film is required, the function of the substrate is sufficiently exhibited. The thickness is made as thin as possible within the range. However, even in such a case, it is usually 10 μm or more from the viewpoints of manufacturing and handling of the substrate, and mechanical strength and the like.

In the present invention, when an electrophotographic photosensitive member is produced, particularly in the case of a non-single crystal photosensitive member containing silicon which is an amorphous silicon photosensitive member, silane (SiH ₄ ), Disilane (Si
₂ H _6), silicon tetrafluoride (SiF _4), include amorphous silicon forming raw material gas or mixed gas thereof, such hexafluoride disilicon (Si ₂ F _6).

Hydrogen (H ₂ ), argon (A
r), helium (He) and the like.

Further, as a characteristic improving gas for changing the band gap width of the deposited film, nitrogen (N ₂ ) or ammonia is used.
Element containing a nitrogen atom such as (NH ₃ ), oxygen (O ₂ ), nitric oxide (NO), nitrogen dioxide (NO ₂ ), nitrous oxide (N ₂ O), carbon monoxide (CO), carbon dioxide An element containing an oxygen atom such as (CO ₂ ), methane (CH ₄ ), ethane (C ₂ H ₆ ), ethylene (C ₂
H ₄ ), acetylene (C ₂ H ₂ ), hydrocarbons such as propane (C ₃ H ₈ ), germanium tetrafluoride (GeF ₄ ), nitrogen fluoride (NF ₃ ).
And the like or a mixed gas thereof.

Further, in the present invention, even if a dopant gas such as diborane (B ₂ H ₆ ), boron fluoride (BF ₃ ), phosphine (PH ₃ ) is simultaneously introduced into the discharge space for the purpose of doping, The invention is equally valid.

At the time of producing the electrophotographic photosensitive member using 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, more preferably 10 μm or more and 70 μm or less, optimal. 15 μm or more,
When the thickness is 50 μm or less, a particularly good image as an electrophotographic photoreceptor can be obtained.

In the present invention, the effect was recognized when the pressure of the discharge space at the time of forming the deposited film was any region.
X10 ^-3 Pa or more, 13.3Pa or less, preferably 13.3 x 10
Above ^-2 Pa and below 6.65 Pa, particularly good effects in terms of discharge stability and deposited film uniformity were obtained with good reproducibility.

In the present invention, the substrate temperature at the time of forming the deposited film is effective in the range of 100 ° C. to 500 ° C., 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.

As the means for heating the substrate in the present invention,
For example, a heating element having a vacuum specification can be used, and more specifically, an electric resistance heating element such as a wound heater of a sheath-shaped heater, a plate heater, a ceramic heater, a heat radiation lamp heating element such as a halogen lamp or an infrared lamp, a liquid, An example of the heating element is a heat exchange means using gas as a heating medium.

As the surface material of the heating means, metals such as stainless steel, nickel, aluminum, copper, ceramics, heat-resistant polymer resin, etc. can be used. In addition to the above, a method of providing a heating-dedicated container separately from the reaction container and heating and then transporting the substrate into the reaction container in a vacuum can also be used. In the present invention, the above means can be used alone or in combination.

In the present invention, the energy for generating plasma may be DC, RF, microwave, or the like. In particular, when microwave is used as the energy for generating plasma, abnormal growth due to surface defects on 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.

In the present invention, when microwave is used for plasma generation, microwave power may be any as long as discharge can be generated, but 100 W or more and 10 kW or less, preferably 500 W or more and 4 kW or less is the main power. It is suitable for carrying out the invention.

In the present invention, it is effective to apply a voltage (bias voltage) to the discharge space when the deposited film is formed, and it is preferable that an electric field be applied at least in the direction in which the cations collide with the substrate. When no bias is applied, the effect of the present invention is significantly reduced. Therefore, the voltage of the DC component is 1 V or higher and 500 V or lower, preferably 5 V or higher and 100.
It is desirable to apply a bias voltage of V or less at the time of forming the deposited film in order to obtain the effects of the present invention.

In the present invention, when microwaves are introduced into the reaction vessel using a dielectric window, the material of the dielectric window is alumina (Al ₂ O ₃ ), aluminum nitride (AlN), boron nitride (BN), Materials such as silicon nitride (SiN), silicon carbide (SiC), silicon oxide (SiO ₂ ), beryllium oxide (BeO), Teflon (registered trademark), and polystyrene, which have little microwave loss, are usually used.

In the deposited film forming method in which the discharge space is surrounded by a plurality of bases, the space between the bases is 1 mm or more and 50 m.
m or less is preferable. The number of bases may be any as long as a discharge space can be formed, but 3 or more, and more preferably 4 or more are suitable.

The present invention can be applied to any electrophotographic photosensitive member manufacturing method. In particular, a base is provided so as to surround a discharge space, and a microwave is introduced from at least one end side of the base by a waveguide. With this configuration, a great effect is obtained when a deposited film is formed.

The electrophotographic photosensitive member manufactured by the method of the present invention is not only used in an electrophotographic copying machine, but also applied to 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 for producing an electrophotographic photosensitive member.

[Experimental Example 1] A cylindrical substrate made of aluminum having a diameter (outer 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 by the procedure, and then the substrate surface was washed. These surface treatments were performed, and an amorphous silicon deposited film was formed on the substrate using the deposited film forming apparatus of the present invention shown in FIG. 1 under the conditions of Table 1, and the blocking type electrophotographic photosensitive having the layer structure shown in FIG. The body was made. At this time, the rotation speed was changed as shown in Table 2. The electrophotographic characteristics of the electrophotographic photosensitive member thus prepared were evaluated as follows.

For the experiment, the copying process speed was set to 2 in advance.
Change it arbitrarily within the range of 00-800mmsec, and add 6-
A voltage of 7 kV was applied to carry out corona charging, a latent image was formed on the surface of the electrophotographic photosensitive member by laser image exposure of 788 nm, and then remodeling was performed so that an image could be formed on the transfer paper by a normal copying process. Canon Copier (NP6
The prepared electrophotographic photosensitive member was put in (650) and the density unevenness of the halftone image was evaluated. At the same time, the image deletion was evaluated. The results are also shown in Table 2.

[Conventional Example 1] As a conventional deposited film forming apparatus,
A device similar to the device of FIG. 1 except that the rotating mechanism is a gear and a motor 214 as shown in FIG. 2, and the water conduit 115 is omitted.
An electrophotographic photosensitive member was prepared by using (the last two digits of the code correspond to each other), and the result when the rotation speed was changed as shown in Table 2 in the same manner as in Experimental Example 1 was also set as "Conventional Example 1". It shows in Table 2.

(Evaluation of image unevenness) A3 graph paper (manufactured by KOKUYO)
On the platen of the copier and changing the aperture of the copier to obtain an image of the exposure amount of the manuscript from the range where the line width of the graph is barely recognized to the point where the white background begins to fog. Then, 10 copies having different densities were output.

These images were observed at a distance of 40 cm from the eyes to check whether a difference in density was recognized, and evaluation was carried out according to the following criteria. ⊚: No image unevenness is observed on any of the copies. ○: There are some copies with uneven image and some with no unevenness. However, all of them are slight and there is no problem at all. Δ: Image unevenness is observed on any copy. However, the image unevenness is slight on at least one copy, and there is no practical problem. X: Large image unevenness is observed on all copies.

(Evaluation of image deletion) The image forming apparatus in which the photosensitive member and the toner as the sample were charged was left in an H / H environment for an appropriate period of 72 hours or more to stabilize the inside of the apparatus in the environment. After that, 50,000 sheets of paper were passed through, and then the apparatus was turned off and left for 24 hours. After leaving, use the chart below to print 100 images continuously.
It was judged based on the image at that time.

Although some models for testing are usually equipped with an environmentally friendly heater (drum heater) or the like, this experiment was carried out with the above heaters or the like removed.

The Iroha chart (Canon test chart: FY9-9058-000) and NA-
7 chart (Canon test chart: FY9-9060-00
0) was used.

Regarding the image deletion, the image is judged by visual inspection including image observation with a microscope, and ⊚ is very good, ∘ is good, Δ is somewhat good, ▲ is no problem in practical use, and X is slightly difficult in practical use. It was divided into 5 ranks.

[0076]

[Table 1]

[0077]

[Table 2]

As is apparent from Table 2, 0.5 rpm or more, 6
Good results were shown in the range of 0 rpm or less.

[Experimental Example 2] As shown in Table 3, a heating mechanism (not shown) provided simply before being introduced into the rotating mechanism was provided,
A blocking electrophotographic photosensitive member was formed on a substrate in the same manner as in Experimental Example 1 except that the temperature of water in the rotating mechanism was intentionally changed, and then the same evaluation as in Experimental Example 1 was performed. The results are also shown in Table 3. (However, the rotation speed of the substrate was 6 rpm)

[0080]

[Table 3]

As is clear from Table 3, good results were shown when the water temperature was 10 ° C or higher and 60 ° C or lower. It was found that if the temperature of the water in the rotating mechanism is too low, condensation on the surface of the electrophotographic photoconductor itself may occur due to condensation (please confirm that this is an error in "condensation".). On the contrary, it was confirmed that if it is too high, the cooling effect on the rotating shaft will be weakened, and the electrophotographic photosensitive member itself will be affected.

[Experimental Example 3] The water path for rotating the substrate was
An electrophotographic photosensitive member was prepared in the same manner as in Experimental Example 1 except that, after the cathode electrode was cooled, water was supplied to the rotating mechanism, which was the reverse of the flow of water shown in FIG. 1. As a result of evaluation by the method described above, the same results as in Experimental Example 1 were obtained.

[Experimental Example 4] The water path for rotating the substrate was changed to
An electrophotographic photosensitive member was prepared in the same manner as in Experimental Example 2 except that, after the cathode electrode was cooled, water was supplied to the rotating mechanism, which was the reverse of the flow of water shown in FIG. As a result of evaluation by the method described above, the same results as in Experimental Example 2 were obtained.

[0084]

EXAMPLES Examples of the present invention will be further described.

Example 1 Using the same aluminum substrate and deposited film forming apparatus as in Experimental Example 1, the blocking type electrophotographic photoreceptor having the layer structure shown in FIG. 6A was formed on the substrate under the conditions shown in Table 4. Was produced.

The electrophotographic characteristics of the electrophotographic photosensitive member thus prepared were evaluated as follows. However, each of 10 photoconductors produced under the same film forming condition was evaluated.

The image evaluation shows the results of the following method in addition to the evaluation of image unevenness and the image deletion performed in Experimental Example 1. Further, a blocking type electrophotographic photosensitive member equivalent to that of Example 1 was manufactured using the conventional apparatus shown in FIG. 2 and evaluated in the same manner as in Example 1, and the results are shown in Table 5 as Conventional Example 2.

[0088]

[Table 4]

(Evaluation of Black Spots and Image Defects) The image sample showing the most image defects among the image samples obtained when the halftone original and the character original are copied on the original table by changing the copying process speed. Was evaluated. As an evaluation method, the image sample was observed with a magnifying glass and evaluated by the state of white dots in the same area. ◎… Good. ○: There is some problem, but there is no problem at all. △: There are slight defects on the entire surface, but there is no problem in practical use. ×: There is a problem with a large defect on the entire surface.

(Evaluation of Electrophotographic Characteristic 1) The surface potential of the photoconductor obtained at the developing position when the same charging voltage is applied at a normal process speed is evaluated as a chargeability by a relative value. However, the charging ability of the electrophotographic photosensitive member obtained in Comparative Example 1 is 100%.

(Evaluation of Electrophotographic Property 2) After the same charging voltage is applied at a normal process speed, the amount of light obtained when light is irradiated and dropped to a certain potential is evaluated as a relative value as sensitivity. However, the charging ability of the electrophotographic photosensitive member obtained in Comparative Example 1 is 100%.

[0092]

[Table 5]

As is clear from Table 5, very good results were shown, and an unexpected effect of improving electrophotographic characteristics could be obtained.

Example 2 Using the same substrate as in Example 1,
After performing the surface treatment in the same manner as in Example 1, FIG.
By using the μwPCVD apparatus shown in FIGS. 6- (A) and 3- (B) under the conditions shown in Table 6, the blocking electrophotographic photosensitive member shown in FIG. 6- (B) was prepared and processed in the same manner as in Example 1. The evaluation results are shown in Table 7. Incidentally, in FIG. 6- (B), 601, 602, 603-
Reference numerals 1, 603-2 and 604 denote an aluminum substrate, a charge injection blocking layer, a charge transporting layer, a charge generating layer, and a surface layer, respectively.

[0095]

[Table 6]

[0096]

[Table 7]

As is apparent from Table 7, the present invention is effective even if the device and layer structure are different.

Example 3 Using the same substrate as in Example 1,
After performing the same surface treatment as in Example 1, V shown in FIG.
Using the HF PCVD equipment and under the conditions shown in Table 8,
A blocking type electrophotographic photosensitive member having the layer structure shown in (B) was prepared and evaluated by the same method. As a result, good results similar to those of Example 1 were obtained.

[0099]

[Table 8]

[0100]

As described above, according to the present invention, for example, a deposited film forming apparatus including a step of forming a functional film on a substrate by a plasma CVD method, particularly an electrophotographic photoconductor using a cylindrical substrate. In the body manufacturing apparatus and method, by rotating the cylindrical substrate with water, it is possible to suppress deterioration in quality due to equipment factors, reduce equipment investment, and improve equipment durability. Therefore, it is possible to inexpensively and stably manufacture an electrophotographic photosensitive member which gives a high-quality and uniform image.

[Brief description of drawings]

FIG. 1 is a schematic vertical sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by an RF plasma CVD method of the present invention.

FIG. 2 is a schematic cross-sectional view of a conventional deposited film forming apparatus used for forming a deposited film on a cylindrical substrate by an RF plasma CVD method using a rotation mechanism of a motor and a gear.

3 (A) is a schematic vertical cross-sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a microwave plasma CVD method using a rotating mechanism of the present invention, and FIG.
(B) is a cross-sectional view taken along line XX of FIG.

FIG. 4 is a schematic vertical cross-sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a microwave plasma CVD method using the motor and gear rotating mechanism of FIG. 4A. 4B is a cross-sectional view taken along line XX of FIG.

FIG. 5 is a schematic vertical sectional view of a deposited film forming apparatus for forming a deposited film on a cylindrical substrate by a VHF plasma CVD method.

6A and 6B are cross-sectional views showing the layer structure of an electrophotographic photosensitive member.

FIG. 7 is a view of the rotating mechanism as viewed from directly below. (AC)
An example in which the outer wall is cylindrical is shown. (A) An example of a rotating mechanism using flat blades is shown (Fig. 1
Those shown in). (B) An example of a rotating mechanism having bent blades is shown (an example of another aspect). (C) An example of a rotating mechanism in which the shaft itself has a notch instead of using a blade is shown (an example of another aspect). (D) This is another embodiment of (A) in which the outer wall is in the shape of a rectangular parallelepiped.

FIG. 8 is a diagram showing a configuration example of a bearing seal. (A) Shows the most common O-ring seal. (B) Shows a metal seal. (C) shows a magnetic fluid seal.

[Explanation of symbols]

101, 201, 301, 401, 501 Reaction vessel 102, 202 Cathode electrode 103, 203 Top plate 104, 204 Base plate 105, 205 Insulator 106, 206, 306, 406, 506 Substrate 108, 208, 303, 403, 503 Heating Heater 109, 209 Raw material gas introduction pipe 111, 211 Raw material gas inflow valve 112, 212 Mass flow controller 114, 302, 502, 700, 710 Rotating mechanism 115 (a, b, c), 312, 509 of water of the present invention Route (water pipe,
Drain pipe) 116,216 High frequency power supply 117,217 Base substrate holder 118,218,304,404,504 Exhaust pipe 119,219,313,413,513,701,8
01 rotary shafts 214, 402 rotation motors 307, 407, 507 discharge spaces 308, 408 raw material gas introduction pipes and DC application electrodes 309, 409 DC power supplies 310, 410 microwave introduction windows 311, 411 waveguide 505 VHF power supply means 508 VHF power source 601 Aluminum substrate 602 Charge injection blocking layer 603 Photoconductive layer 603-1 Charge transport layer 603-1 Charge generation layer 604 Surface layer 702 Blade (flat plate) 703 Blade (curved surface) 711 Rotating shaft (notched) 712 Notched portion 714 Flow path 800 Bearing 802 O-ring 803 Metal seal 804 Magnetic fluid

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hideaki Matsuoka             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Kazuhiko Takada             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Koji Obishi             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 4K030 AA06 BA30 BB12 CA02 CA16                       FA01 GA07 KA05 LA17

Claims (10)

[Claims] 1. A reaction chamber which can be hermetically sealed, a substrate holder for placing a cylindrical substrate in the reaction chamber, and a deposited film for vapor-depositing a deposited film on a cylindrical substrate arranged in the substrate holder. In the apparatus for producing a vapor-deposited film having a forming means, the substrate holder has a substrate rotating mechanism for rotating a cylindrical substrate installed in the substrate holder around its central axis by using hydraulic power. An apparatus for producing a deposited film, characterized by: 2. The manufacturing apparatus according to claim 1, wherein the reaction chamber is airtight under reduced pressure, and the deposited film forming means forms a deposited film by a reduced pressure vapor deposition method. 3. The manufacturing apparatus according to claim 1, wherein the deposited film is amorphous. 4. The production apparatus according to claim 1, wherein the reaction chamber has a cooling means using cooling water for the reaction chamber, and the water power is obtained by a water flow of the cooling water. . 5. A structure in which an inner wall of the reaction chamber constitutes a cathode electrode, and a cylindrical substrate provided on the substrate holder constitutes an anode electrode, and discharge can be generated between these electrodes. The manufacturing apparatus according to claim 4, which has the cooling water for cooling at least an inner wall of the reaction chamber. 6. A method for producing a deposited film by introducing a source gas into a closed reaction chamber in which a cylindrical substrate is arranged to vapor-deposit the deposited film on the cylindrical substrate, the method comprising the steps of: A method for producing a deposited film, which comprises vapor-depositing the deposited film while rotating the substrate around its central axis by using hydrodynamic power. 7. The manufacturing method according to claim 6, wherein the vapor phase growth of the deposited film is performed under reduced pressure. 8. The manufacturing method according to claim 6, wherein the deposited film is amorphous. 9. The production method according to claim 6, wherein the reaction chamber is cooled by using cooling water for the reaction chamber, and the water power is obtained by a water flow of the cooling water. 10. The inner wall of the reaction chamber constitutes a cathode electrode, the cylindrical substrate constitutes an anode electrode, discharge is performed between these electrodes, and the cooling water is at least the inner wall of the reaction chamber. The manufacturing method according to claim 9, wherein the method is for cooling.