JPH093652A - Deposited film forming apparatus by plasma CVD method - Google Patents

Abstract

(57) [Abstract] [Objective] The present invention balances the flow rate and speed of gas in a reaction vessel to obtain a uniform film, drastically reduces the occurrence of image defects, and dramatically improves the yield. An object of the present invention is to provide a deposited film forming apparatus by the plasma CVD method, which can be mass-produced. According to the present invention, in order to achieve the above object, the raw material gas introducing pipe corresponding to a lower end of a cylindrical support constituting a deposited film forming apparatus has a lower portion corresponding to an upper end of the cylindrical support. The raw material gas introduction pipe is provided so as to be inclined with respect to the longitudinal direction of the cylindrical support so that the distance from the upper part of the gas introduction pipe to the cylindrical support becomes smaller on the coaxial outer circumference thereof, In addition to obtaining such a film, the number of image defects is drastically reduced and the yield is dramatically improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a functional deposited film, particularly an electrophotographic photosensitive member, formed on a support by a plasma CVD method.
The present invention relates to an improved deposited film forming apparatus for continuously forming a crystalline or non-single crystalline semiconductor, which can be suitably used as a semiconductor element such as a photovoltaic device, an image input line sensor, an imaging device, and a TFT. In particular, it relates to an apparatus for forming a large-area deposited film such as an electrophotographic photoreceptor.

[0002]

2. Description of the Related Art Conventionally, as an element member used for a semiconductor device, a photoreceptor for electrophotography, a line sensor for image input, an imaging device, a photovoltaic device, other various electronic elements and optical elements, amorphous silicon,
For example, amorphous silicon compensated with hydrogen or / and halogen (for example, fluorine, chlorine, etc.) [hereinafter, AS
abbreviated as i (H.X)] or a crystalline deposited film such as a diamond thin film, some of which have been put to practical use. Then, such a deposited film is formed by a plasma CVD method, that is,
Source gas is decomposed by direct current or high frequency, or glow discharge by microwave, and formed by a method of forming a deposited film on a support such as glass, quartz, heat-resistant synthetic resin film, stainless steel, aluminum, etc. Various proposals have been made. For example, FIG. 2 is a schematic configuration diagram showing an example of an apparatus for manufacturing an electrophotographic photosensitive member by a high frequency plasma CVD method (hereinafter abbreviated as “PCVD”). The configuration of the manufacturing apparatus shown in FIG. 2 is as follows. This apparatus is roughly classified into a deposition apparatus (2100), a source gas supply apparatus (2200), and a reaction vessel (2111).
It is composed of an exhaust device (not shown) for reducing the pressure inside. The reaction vessel (211) in the deposition apparatus (2100)
A cylindrical support (2112), a heater for heating the support (2113), a raw material gas introduction pipe (2114) are installed in the inside of 1), and a high frequency matching box (2115) is further connected. The source gas supply device (2200) is S
iH4, GeH4, H2, CH4, B2H6, PH3 and other source gas cylinders (2212-1226) and valve (223)
1-22236, 2241-2246, 2251-225
6) and mass flow controller (2211-22)
16), and each source gas cylinder has a valve (2
It is connected to the gas introduction pipe (2114) in the reaction vessel (2111) via 260).

The formation of a deposited film using such a conventional deposited film forming apparatus is performed, for example, as follows. First,
The cylindrical support (2112) is installed in the reaction vessel (2111), and the inside of the reaction vessel (2111) is evacuated by an exhaust device (for example, a vacuum pump) not shown. Then, the cylindrical support (211) is heated by the heater (2113) for heating the support.
The temperature of 2) is controlled to a predetermined temperature of 20 ° C to 450 ° C. In order to allow the source gas for forming the deposited film to flow into the reaction vessel (2111), a valve (2231 to 223) of a gas cylinder is used.
37), confirming that the leak valve (2117) of the reaction vessel is closed, and checking the inflow valves (2241 to 2241).
246), the outflow valves (2251-2256) and the auxiliary valve (2260) are confirmed to be open, and the main valve (2118) is first opened to open the reaction vessel (211).
1) and the inside of the gas pipe (2116) is exhausted. Next, when the reading of the vacuum gauge (2119) became about 5 × 10 ⁻⁶ Torr, the auxiliary valve (2260) and the outflow valve (225
1 to 2256) are closed. Then, the gas cylinder (222
1 to 2226) from each gas valve (2231 to 223)
6) is opened and introduced, and the pressure regulator (2261-226)
Each gas pressure is adjusted to ² Kg / cm ² by 6). Next, the inflow valves (2241 to 2246) are gradually opened to allow the respective gases to flow through the mass flow controllers (2211 to 2).
216).

After the preparation for film formation is completed as described above, each layer is formed by the following procedure. Cylindrical support (2
When the temperature reaches a predetermined temperature, the outflow valve (2)
251 to 2256) and the auxiliary valve (2260) are gradually opened, and the gas cylinder (2221 to
2226), a predetermined gas is introduced into the reaction vessel (2111) via the gas introduction pipe (2114). Next, the mass flow controllers (2211 to 2216) are adjusted so that each raw material gas has a predetermined flow rate. that time,
The opening of the main valve (2118) is adjusted while watching the vacuum gauge (2119) so that the pressure in the reaction vessel (2111) becomes a predetermined pressure of 1 Torr or less. When the internal pressure is stabilized, a high-frequency power source (not shown) having a frequency of 13.56 MHz is set to a desired power, and high-frequency power is introduced into the reaction vessel (2111) through the high-frequency matching box (2115) to generate glow discharge. Let it. The source gas introduced into the reaction vessel is decomposed by the discharge energy, and a deposited film mainly containing predetermined silicon is formed on the cylindrical support (2112). After the formation of the desired film thickness, the supply of the high-frequency power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed. By repeating the same operation a plurality of times, a light receiving layer having a desired multilayer structure can be formed. When forming each layer, it goes without saying that all outflow valves other than the necessary gas are closed, and each gas is supplied to the reaction vessel (211).
1) Close the outflow valves (2251 to 2256), open the auxiliary valve (2260) and open the main valve to avoid remaining in the piping from the outflow valves (2251-2256) to the reaction vessel (2111). Valve (21
18) is fully opened and the system is once evacuated to a high vacuum, if necessary.

In this way, when forming a deposited film having a large area, such as an electrophotographic photoreceptor, it is necessary to make the film thickness and film quality uniform, and various apparatus configurations have been proposed for that purpose. For example, according to Japanese Patent Application Laid-Open No. 58-30125, a gas pipe for gas introduction, which is independent of a cylindrical electrode, is used for introducing a raw material gas, and the cross-sectional area and interval of the gas release holes provided in the gas pipe are set. A technique is disclosed in which the film thickness and image unevenness when used as a photoconductor for electrophotography are improved by changing the lengthwise direction of a cylindrical support and uniformly discharging a raw material gas. According to Japanese Patent Application Laid-Open No. 58-32413, the raw material gas is rotated in a fixed direction in the direction of the gas release hole in both the cylindrical electrode also serving as the gas introducing means and the case where the gas introducing gas pipe is used. There is disclosed a technique for improving the uniformity of the film thickness by setting the above. Japanese Patent Application Laid-Open No. Sho 62-218573 discloses a technique for improving the uniformity of the film thickness and the film quality without rotating the support by connecting the upper and lower portions of the gas introduction pipe with branch pipes. ing. According to Japanese Patent Laid-Open No. 63-479, the relationship between the angle between the gas discharge hole of the gas introduction tube and the cylindrical support, the inner diameter of the cylindrical electrode, and the inner diameter of the cylindrical support is defined. A technique for improving the uniformity of film thickness and film quality without rotating the support is disclosed.
According to Japanese Patent Application Laid-Open No. 63-7373, by using a gas introduction pipe and defining the relationship between the cross-sectional area of the gas introduction pipe and the cross-sectional area and number of the gas discharge holes, the cylindrical support can be rotated without rotating. A technique for making the thickness and quality of the deposited film uniform has been disclosed. These techniques have improved the uniformity of the film thickness and film quality of the electrophotographic photoconductor, and the yield has been improved accordingly.

[0006]

However, the photoreceptor for electrophotography made by the conventional apparatus has been improved in terms of the yield and the uniformity of the film thickness and film quality. In fact, there is room for further improvement in planning. In particular, high image quality, high speed, and high durability of electrophotographic devices are rapidly progressing, and in the electrophotographic photoreceptor, with further improvement of electric characteristics and photoconductive characteristics, charging ability,
There is a need to significantly increase performance in all environments while maintaining sensitivity. Improvements in the optical exposure device, developing device, transfer device, and the like in the electrophotographic apparatus have been made in order to improve the image characteristics of the electrophotographic apparatus. Is now available. Under such circumstances, the above-mentioned conventional technology has made it possible to achieve a certain degree of uniformity of film thickness and film quality with respect to the above-mentioned problems, but it cannot be said that further improvement in image quality is still sufficient. In particular, as a challenge to further improve the image quality of the amorphous silicon type photoreceptor,
It is possible to obtain a uniform film and suppress the generation of minute image defects. For that purpose, it is necessary to balance the flow rate and velocity of the gas in the reaction space. In addition, a film or the like attached to the raw material gas introduction pipe during film formation scatters on the support, and the deposited film abnormally grows, causing minute image defects on the image. Therefore, it is necessary to prevent the products such as the film adhered to other than the support from scattering to the support.

Therefore, the present invention solves various problems in the above-described conventional deposited film forming apparatus, balances the flow rate and speed of the gas in the reaction vessel, and obtains a uniform film.
It is an object of the present invention to provide a deposited film forming apparatus by the plasma CVD method, which can drastically reduce the generation of image defects, dramatically improve the yield, and perform mass production.

[0008]

According to the present invention, in order to achieve the above-mentioned object, the lower part of the source gas introducing pipe corresponding to the lower end of the cylindrical support constituting the deposited film forming apparatus is the cylindrical support. The raw material gas introduction pipe is inclined with respect to the longitudinal direction of the cylindrical support so that the distance from the upper portion of the raw material gas introduction pipe corresponding to the upper end to the cylindrical support becomes smaller on its coaxial outer circumference. The gas amount in the reaction vessel can be balanced by providing the above. That is, the present invention is a cylindrical reaction container having a reaction space, a cylindrical support provided in the reaction space, on the coaxial outer periphery of the cylindrical support along the longitudinal direction of the cylindrical support. In a deposited film forming apparatus comprising a plurality of deposited film forming raw material gas introduction pipes provided, discharge energy applying means for exciting the raw material gas to generate excited species, and means for exhausting the reaction chamber, The distance b between the lower portion of the raw material gas introduction pipe corresponding to the lower end of the cylindrical support and the cylindrical support is the upper portion of the raw material gas introduction pipe corresponding to the upper end of the cylindrical support and the cylindrical support. With respect to the longitudinal direction of the cylindrical support, the raw material gas introduction pipe is preferably set to be 0.6a so as to be smaller than the distance a on the coaxial outer circumference.
≦ b ≦ 0.95a, more preferably 0.80a ≦ b ≦
It is characterized in that it is provided so as to be inclined in the relation of 0.9. Further, the present invention provides a means for inclining a gas introduction pipe on the coaxial outer circumference of the cylindrical support, wherein the upper end of the raw material gas introduction pipe is in close contact with the cathode electrode of the discharge energy applying means, and the raw material gas A ceramic ring for fixing the introduction tube is mounted, and the surface roughness (Rz) of the ceramic ring is preferably 10 to 1
It is characterized in that the thickness is 00 μm, more preferably 15 to 60 μm. Further, in the present invention, when the gas introduction is performed from the upper part of the reaction vessel, the ceramic ring can be configured to also serve as the gas introduction branch pipe.

[0009]

The inventors of the present invention have conducted intensive studies to overcome the above-mentioned problems in the conventional deposited film forming method and achieve the above-mentioned object of the present invention. It was found that the film quality and mass production can be improved by changing the distance to the cylindrical support within a predetermined range. That is, a gas introduction pipe having a plurality of gas emission holes is used to release the raw material gas into the discharge space, and the distance between the lower portion of the gas introduction pipe (the portion corresponding to the lower end of the cylindrical support) and the cylindrical support ( b) is smaller than the distance (a) between the upper portion of the gas introduction pipe (the portion corresponding to the upper end of the cylindrical support) and the cylindrical support on the outer circumference coaxial with the cylindrical support,
It was found that the inclination of the gas introduction pipe with respect to the longitudinal direction of the cylindrical support significantly affects the uniformity of the deposited film. As a means for inclining the gas introduction pipe, a ceramic ring is attached to the upper end of the gas introduction pipe to suppress a film or the like attached to the spherical surface of the upper end of the gas introduction pipe during formation of the deposited film, that is, the gas during formation of the deposited film. It was also found that the scattering of film pieces or the like from the upper spherical surface of the introduction tube to the support is eliminated, and that they are effective in suppressing image defects caused by abnormal growth of the deposited film by using them as nuclei. That is, the ceramic ring is attached to the upper end of the gas introduction pipe, and the distance (a) on the upper side of the gas introduction pipe
On the other hand, it was found that by setting the distance (b) on the lower side of the gas introduction pipe within a specific range, the quality and thickness of the deposited film can be made uniform, and image defects can be drastically reduced. . The present invention has been completed based on these findings.

This will be described in detail below with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing an arrangement of a counter electrode including a cylindrical reaction vessel also serving as an electrode and a cylindrical support, and a cylindrical support in a deposition film forming apparatus using a plasma CVD method of the present invention. In the figure, 101 is a cylindrical reaction vessel, 102 is a counter electrode including a cylindrical support, 103 is a gas introduction pipe, 104 is a ceramic ring, 105 is an exhaust pipe, and 106 is a gas introduction branch pipe. The distance between the cylindrical support and the gas introduction pipe is a (horizontal distance from the upper end of the cylindrical support to the gas introduction pipe) for the upper side, and b (for the cylindrical support) for the lower side. The distance from the lower end to the gas introduction pipe in the horizontal direction), and the distance on the lower side is specified within a specific range. In the conventional device, the gas introduction pipe was installed parallel to the support in the longitudinal direction, but since the exhaust gas is from the bottom, the amount of gas in the reaction space becomes non-uniform up and down, and the length of the cylindrical support increases. There is a problem that the film thickness and the film quality vary in the direction. To solve these problems,
Although the distribution of the gas release holes provided in the gas introduction pipe and the adjustment of the gas release direction were adjusted to some extent, it was still insufficient. In addition, the film deposited on the upper spherical surface of the gas introduction pipe is scattered to the cylindrical support, so that the deposited film grows abnormally,
There is also the problem of causing image defects.

In the apparatus for forming a deposited film by the plasma CVD method of the present invention, the distance (b) between the gas introduction tube and the lower side of the upper side (a) is preferably 0.6a≤b≤.
0.95a, more preferably in the range of 0.8a ≦ b ≦ 0.9a with an inclination (closer to the lower side) to the cylindrical support, so that The amount of gas can be increased without changing the amount of release, and the film thickness and film quality of the deposited film on the cylindrical support can be made uniform. Further, as a means for inclining the gas introducing pipe in the longitudinal direction on the coaxial outer periphery with respect to the cylindrical support, a ceramic ring can be closely attached to the cathode electrode at the upper end of the gas introducing pipe to position the gas introducing pipe. By mounting it in a shape, you can accurately determine the position,
In addition, it is possible to suppress image defects due to film scattering from the upper spherical surface of the gas introducing pipe. The surface roughness of the ceramic ring is preferably 10 to 100 μm,
More preferably, the range of 15 to 60 μm is suitable for the present invention. Further, even when gas is introduced from the upper part of the reaction space, the ceramic ring can be used as a gas introduction branch pipe as shown in FIG.

The support used in the present invention may be either electrically conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au, In, Nb, T
e, V, Ti, Pt, Pd, Fe, and the like, as well as alloys thereof, such as stainless steel, are included. Also, at least the surface of the electrically insulating support such as a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, etc., at least on the side on which the light-receiving layer is formed, such as a glass or ceramic. Can be used. The shape of the support used in the present invention may be a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface, and the thickness thereof can form a desired electrophotographic photoreceptor. When the flexibility as the electrophotographic photoreceptor is required, the thickness can be made as thin as possible within the range in which the function as the support can be sufficiently exerted. However, the thickness of the support is usually 10 μm or more in terms of production, handling, mechanical strength and the like. In particular, when performing image recording using coherent light such as laser light, unevenness is provided on the surface of the support in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in visible images. May be. The unevenness provided on the surface of the support is described in JP-A-6-63.
It is prepared by a known method described in JP-A-0-168156, JP-A-60-178457, JP-A-60-225854 and the like. Further, as another method for more effectively eliminating image defects due to interference fringe patterns when using coherent light such as laser light, a concave-convex shape formed by a plurality of spherical trace depressions may be provided on the surface of the support. . That is, the surface of the support has irregularities finer than the resolution required for the electrophotographic photosensitive member, and the irregularities are due to a plurality of spherical trace depressions. The unevenness due to a plurality of spherical trace depressions provided on the surface of the support is disclosed in JP-A-61-23.
It is created by a known method described in Japanese Patent No. 1561. To form a deposited film by the glow discharge method using the apparatus of the present invention, basically, a source gas for supplying Si, which can supply silicon atoms (Si), and hydrogen atoms (H), can be supplied. A raw material gas for H supply or / and a raw material gas for X supply capable of supplying a halogen atom (X) are introduced into the reaction vessel in a desired gas state to cause glow discharge in the reaction vessel, It suffices to form a layer of a-Si: H, X on a predetermined support which is installed at a predetermined position in advance.

Si supply gas used in the present invention
Possible substances include SiH4, Si2H6, Si3H
8, hydrogen in gas state such as Si4H10, or gasifiable
Examples of effective use of silicon oxide (silanes)
In addition, it is easy to handle when creating layers and has good Si supply efficiency.
From the standpoint of size, SiH4 and Si2H6 are preferred.
You can Then, hydrogen atoms are formed in the formed deposited film.
Introduced artificially, more control of the introduction ratio of hydrogen atoms
Membrane characteristics that are easily scaled to achieve the object of the present invention
To obtain H2 and / or
Desired amount of He or silicon compound gas containing hydrogen atoms
It is necessary to mix and form layers. In addition, each gas
It is possible to mix not only single species but also multiple species at a prescribed mixing ratio.
It does not support. In addition, the
Even if it is effective as a raw material gas for supplying rogen atoms,
For example, halogen gas, halide, halogen containing halogen
Compounds such as intermetallic compounds and silane derivatives substituted with halogen.
Preference is given to those in the form of soot or gasifiable halogen compounds.
You can In addition, silicon atoms and halogen atoms
A gaseous or gasifiable halo composed of and
Silicon hydride compounds containing a gen atom are also listed as effective.
I can do it. Halo which can be preferably used in the present invention
Specific examples of the gen compound include fluorine gas (F2) and B
rF, ClF, ClF3, BrF3, BrF5, IF3, I
An interhalogen compound such as F7 can be mentioned. Halo
A silicon compound containing a gen atom, a so-called halogen atom
Specific examples of the substituted silane derivative include, for example,
SiF 4, Si 2F As silicon fluoride such as 6 is preferable
Can be mentioned. Hydrogen atoms contained in the deposited film
Or / and controlling the amount of halogen atoms, for example
Carrier temperature, containing hydrogen atoms and / or halogen atoms
Introduce the raw material used to
The amount of discharge, the discharge power, etc. may be controlled.

In the present invention, it is preferable that the deposited film contain atoms for controlling the conductivity, if necessary.
Atoms that control conductivity may be contained in the deposited film in a uniformly distributed state, or may be contained in a non-uniformly distributed state in the layer thickness direction. . Examples of the atoms that control the conductivity include so-called impurities in the field of semiconductors, and atoms that belong to Group IIIb of the Periodic Table (hereinafter abbreviated as “Group IIIb atoms”) that give p-type conductivity, or An atom belonging to Group Vb of the periodic table which gives n-type conduction characteristics (hereinafter referred to as “Vb
(Abbreviated as "group atom") can be used. III
Specific examples of the b-group atom include boron (B), aluminum (Al), gallium (Ga), and indium (I).
n), thallium (Tl), etc., especially B, Al, Ga
Is preferred. Specific examples of the Group Vb atom include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like, with P and As being particularly preferable. As the content of atoms that control the conductivity contained in the deposited film,
It is preferably 1 × 10 ⁻² to 1 × 10 ⁴ atomic ppm, more preferably 5 × 10 ^{−2 to} 5 × 10 ³ atomic ppm, most preferably 1 × 10 ⁻¹ to 1 × 10 ³ atomic ppm. Is desirable. To structurally introduce a conductivity controlling atom, for example, a group IIIb atom or a group Vb atom, a raw material for introducing a group IIIb atom or a group Vb atom for introducing a group IIIb atom is formed during layer formation. The raw material may be introduced in a gas state into the reaction vessel together with another gas for forming a deposited film. As a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom, a gaseous substance at room temperature and normal pressure or a substance which can be easily gasified under at least a layer forming condition is adopted. Is desirable. Specific examples of the group IIIb atomic substance include B2H6, B4H10, and B5H for introducing a boron atom.
9, boron hydrides such as B5H11, B6H10, B6H12 and B6H14, and boron halides such as BF3, BCl3 and BBr3. In addition, AlCl3, GaCl3, Ga (C
H3) 3, InCl3, TlCl3 and the like can also be mentioned. Effectively used as a raw material for introducing a Group Vb atom is a hydrogen atom such as PH3, P2H4, PH4I, PF3, PF5, PCl3, PCl for introducing a phosphorus atom.
5, halogenated halogens such as PBr3, PBr5, PI3 and the like. In addition, AsH3, AsF3, AsCl3, AsB
r3, AsF5, SbH3, SbF3, SbF5, SbCl
3, SbCl5, BiH3, BiCl3, BiBr3 and the like can also be mentioned as effective starting materials for introducing Group Vb atoms. If necessary, the raw materials for introducing atoms for controlling the conductivity may be replaced by H2 and / or He.
May be used after dilution.

In order to achieve the object of the present invention and form a deposited film having desired film characteristics, the mixing ratio of the gas for supplying Si and the diluting gas, the gas pressure in the reaction vessel, the discharge power and the support. It is necessary to set the temperature appropriately. The flow rate of H2 and / or He used as a diluent gas is appropriately selected in an optimum range according to the layer design. However, H2 and / or He is usually 3
-20 times, preferably 4-15 times, and optimally 5-10 times. Similarly, the gas pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, it is 1 × 10 ^{−4 to} 10 Torr, preferably 5 × 10 ^{−4 to} 5 Torr, most preferably 1 × 10 ^{−. 3 to} lTo
It is preferably rr. Similarly, the discharge power is also appropriately selected according to the layer design, but the discharge power relative to the flow rate of the gas for supplying Si is usually 2 to 7
It is desirably set to a range of 2.5 times, preferably 2.5 to 6 times, and optimally 3 to 5 times. Furthermore, the temperature of the support is
The optimum range is appropriately selected according to the layer design, but it is desirably 200 to 350 ° C. in a normal case. In the present invention, the above-mentioned range is mentioned as a desirable numerical range of the temperature of the support and the gas pressure for forming the deposited film, but these conditions are usually not independently determined separately, It is desirable to determine the optimum value based on mutual and organic relevance in order to form an electrophotographic photoreceptor having characteristics.

Hereinafter, the apparatus of the present invention will be described in more detail with reference to experimental examples and examples, but the present invention is not limited thereto.

(Experimental Example 1) Length 358 mm, outer diameter φ10
Al holder (1000 mm in length) on which an Al cylinder (cylindrical support) with an 8 mm mirror finish is placed
And a photoreceptive layer comprising a charge injection blocking layer, a photoconductive layer and a surface layer on the support using the apparatus shown in FIG.
It was formed under the manufacturing conditions shown in. In this experimental example, the distance between the raw material gas introduction pipe and the cylindrical support was created under the following conditions. Hereinafter, the distance (a) between the upper portion of the raw material gas introduction pipe (the portion corresponding to the upper end of the cylindrical support) and the cylindrical support is referred to as “upper side distance (a)” or “a”, and the raw material gas introduction The distance (b) between the lower part of the tube (the portion corresponding to the lower part of the cylindrical support) and the cylindrical support is referred to as the “lower side distance (b)” or “b”. (1) Lower distance (b) from 0.5 (a) to 0.98
The slope was changed by changing between (a). The distance (a) in this example is 56 mm. (2) The distance on the lower side was (b) = (a), which was parallel to the cylindrical support, and was (a) = 56 mm.

[0018]

[Table 1] The film thickness unevenness and charging potential unevenness of the produced electrophotographic photosensitive member were evaluated. The results are shown in Table 2. As is clear from Table 2, a good electrophotographic photosensitive member was obtained within the range of 0.6a ≦ b ≦ 0.95a. Furthermore, 0.8a ≦ b ≦ 0.9
It was found to be more effective in the range of a.

[0019]

[Table 2] The evaluation method is as follows. "Thickness unevenness" The thickness of the deposited film is measured along the longitudinal direction of the electrophotographic photosensitive member, and the variation in the average value of the thickness is within 3% ◎, within 5% ◯, A three-level evaluation was carried out with a value exceeding 5% as Δ. "Charging potential unevenness" Electrophotographic device (Canon NP615
0 was modified for testing), the prepared electrophotographic photosensitive member was set, and the charging potential was measured in the longitudinal direction of the electrophotographic photosensitive member. A three-point evaluation was performed in which the charge potential variation from the average potential was within 3%, ◎ was within 5%, and ○ was over 5%.

(Experimental Example 2) Length 358 mm, outer diameter φ10
Al holder (1000 mm in length) on which an Al cylinder (cylindrical support) with an 8 mm mirror finish is placed
A light-receiving layer composed of a charge injection blocking layer, a photoconductive layer and a surface layer was formed on the support by using the apparatus shown in FIG. In this experimental example, the raw material gas introduction pipe was tilted so that the distance (b) on the lower side was 0.9a, and a ceramic ring having different surface roughness was mounted on the upper portion of the raw material gas introduction pipe to prepare under the following conditions. . (1) The surface roughness (Rz) of the ceramic ring is 6.3μ.
It was changed from m to 150 μm. (2) No ceramic ring.

The electrophotographic photoreceptor thus produced was evaluated in the same manner as in Experimental Example 1 and the number and size of defects. Table 3 shows the results. As is clear from Table 3,
A good electrophotographic photoreceptor was obtained in the range of 10 to 100 μm. Further, it was found that it is more effective in the range of 15 to 60 μm.

[0022]

[Table 3] The evaluation method for defects is as follows. The surface of the electrophotographic photosensitive member was observed with a "defect" optical microscope at a magnification of 50 times in the range of 9 cm ² , and the size and the number were evaluated. If there are less than 20 defects of 20 μm or more and no defects of 40 μm or more, ◎, 20 μ
There were 20 or more defects of m or more, but no defects of 40 μm or more were evaluated as ◯, and those of 20 or more defects of 20 μm or more and those of 40 μm or more were evaluated as 3 grades. The configuration of the present invention was determined by the above experimental example. Next, the present invention will be described more specifically with reference to Examples and Comparative Examples.

[0023]

【Example】

Example 1 Using an Al holder (length 1000 mm) on which a mirror-finished Al cylinder (cylindrical support) having a length of 358 mm and an outer diameter of φ108 mm was placed, the structure shown in FIG.
On the support, a photoreceptive layer including a charge injection blocking layer, a photoconductive layer and a surface layer was formed under the production conditions shown in Table 4 using the apparatus shown in FIG.

[0024]

[Table 4] The produced electrophotographic photosensitive member was evaluated for film thickness unevenness, charging potential unevenness, and defects. Table 5 shows the results. The evaluation method was the same as in Experimental Example 2.

(Comparative Example 1) Compared with Example 1, in this Comparative Example, electrophotography was carried out under the same conditions as in Example 1 except that the gas introduction tube was installed parallel to the cylindrical support and no ceramic ring was used. A photoconductor was prepared. The produced electrophotographic photosensitive member was evaluated by the same means as in Example 1. The results of these evaluations are shown in Table 5 together with Example 1. The electrophotographic photosensitive member manufactured by the electrophotographic manufacturing apparatus of the present invention showed very good results in all items as compared with the electrophotographic photosensitive member manufactured by the conventional apparatus.

[0026]

[Table 5] Example 2 Using the device described in Example 1, under the manufacturing conditions shown in Table 6, a charge injection blocking layer, a charge transport layer, a charge generation layer,
When an electrophotographic photosensitive member including a surface layer was produced and evaluated in the same manner as in Example 1, good results were obtained as in Example 1.

[0027]

[Table 6] [Embodiment 3] Using the device described in Embodiment 1, under the manufacturing conditions shown in Table 7, a charge injection blocking layer, a charge transport layer, a charge generation layer,
When an electrophotographic photosensitive member including an intermediate layer and a surface layer was prepared and evaluated in the same manner as in Example 1, good results were obtained as in Example 1.

[0028]

[Table 7] [Example 4] An Al holder (length 1000 mm) on which a mirror-finished Al cylinder (cylindrical support) having a length of 358 mm and an outer diameter of 108 mm was mounted was used, and FIG.
A photoreceptive layer comprising a charge injection blocking layer, a photoconductive layer and a surface layer was prepared on the support by using the apparatus shown in Fig. 4, and the same evaluation as in Example 1 was carried out. Good results were obtained as in Example 1.

[0029]

As described above, according to the present invention, the raw material gas introducing pipe is provided so as to be inclined with respect to the longitudinal direction of the cylindrical support,
By changing the distance of the raw material gas introduction pipe to the cylindrical support within a predetermined range, it becomes possible to properly balance the amount of gas in the reaction vessel, and to make the film quality uniform,
The physical properties of the film formed by drastically reducing the occurrence of image defects,
The deposition rate, its reproducibility and productivity can be improved, and the yield can be dramatically improved when mass production is performed.

[Brief description of drawings]

FIG. 1 shows a cylindrical reaction container that also serves as an electrode, a counter electrode including a cylindrical support, a gas introducing pipe tilting means (ceramic ring), and a gas introducing branch pipe in a deposited film forming apparatus by the plasma CVD method of the present invention. It is a schematic explanatory view.

FIG. 2 is an example of an apparatus for forming a light-receiving layer of an electrophotographic light-receiving member of the present invention, which is a schematic explanatory view of an apparatus for manufacturing an electrophotographic light-receiving member by a glow discharge method using high frequency. is there.

FIG. 3 shows a cylindrical reaction container that also serves as an electrode, a counter electrode including a cylindrical support, and a gas introducing pipe tilting means (a gas introducing branch pipe also serving as a ceramic ring) in a deposited film forming apparatus by the plasma CVD method of the present invention. It is a schematic explanatory view shown.

[Explanation of symbols]

 Reference Signs List 101 cylindrical reaction container that also serves as an electrode 102 counter electrode including a cylindrical support 103 gas introduction pipe 104 ceramic ring 105 exhaust pipe 106 gas introduction branch pipe 107 gas introduction branch pipe / ceramic ring 2100 deposition device 2111 reaction vessel 2112 cylindrical support Body 2113 Support heating heater 2114 Raw material gas introduction pipe 2115 Matching box 2116 Raw material gas pipe 2117 Reaction vessel leak valve 2118 Main exhaust valve 2119 Vacuum gauge 2200 Raw material gas supply device 2211 to 2216 Mass flow controller 2221 to 2226 Raw material gas cylinder 2231 to 2236 Raw material Gas cylinder valve 2241 to 2246 Gas inflow valve 2251 to 2256 Gas outflow valve 2261 to 2266 Pressure regulator

Claims (5)

[Claims] 1. A cylindrical reaction container having a reaction space, a cylindrical support provided in the reaction space, and a cylindrical support on the coaxial outer periphery of the cylindrical support along the longitudinal direction of the cylindrical support. In a deposited film forming apparatus comprising a plurality of deposited film forming raw material gas introduction pipes provided, discharge energy applying means for exciting the raw material gas to generate excited species, and means for exhausting the reaction chamber, The lower part of the raw material gas introduction pipe corresponding to the lower end of the cylindrical support is located on the same coaxial outer circumference as the distance from the upper part of the raw material gas introduction pipe corresponding to the upper end of the cylindrical support to the cylindrical support. 2. The apparatus for forming a deposited film by a plasma CVD method, wherein the source gas introduction pipe is provided so as to be inclined with respect to the longitudinal direction of the cylindrical support so as to be smaller in. 2. The raw material gas introducing pipe corresponding to the upper end of the cylindrical support, where b is the distance between the lower portion of the raw material gas introducing pipe corresponding to the lower end of the cylindrical support and the cylindrical support. When the distance between the upper part of and the cylindrical support is a,
The deposited film forming apparatus by the plasma CVD method according to claim 1, wherein the relationship between the distances is set to 0.6a ≦ b ≦ 0.95a. 3. A means for providing the raw material gas introduction pipe inclining with respect to the longitudinal direction of the cylindrical support, wherein the upper end of the raw material gas introduction pipe is in close contact with the cathode electrode of the discharge energy applying means and the The deposited film forming apparatus by the plasma CVD method according to claim 1 or 2, further comprising a ceramic ring for fixing the source gas introduction pipe. 4. The surface roughness (R) of the ceramic ring.
The deposited film forming apparatus by the plasma CVD method according to claim 3, wherein z) is 10 to 100 μm. 5. The deposited film forming apparatus according to claim 3, wherein the ceramic ring also serves as a gas introduction branch pipe.