JP2000054144A - Formation of deposited film by plasma cvd method and device therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To uniformize the balance of the gas to be released from a gas releasing hole provided on the outer pipe of a double pipe into a reaction space in circumferential direction of a reaction vessel by providing a gas distribution pipe feeding a gaseous raw material from a gaseous raw material feeding source to plural gaseous raw material introducing pipes, making this distribution pipe of a double pipe structure and connecting the inner pipe of the double pipe to the gaseous raw material feeding source. SOLUTION: The gas distribution pipe feeding a gaseous raw material from a gaseous raw material feeding source to plural gaseous raw material introducing pipes 104 is made to have a double pipe structure composed of an inner pipe 120 and an outer pipe 103. The inner pipe 120 of the double pipes is connected to the gaseous raw material feeding source, and a gaseous raw material is introduced into the inner pipe 120, thereby, the gaseous raw material is released into a reaction space via a gas releasing hole in the gaseous raw material introducing pipe 104 connected to the outer pipe 103 of the double pipe. At this time, the angle of the gas releasing hole in the inner pipe 120 is made 45 to 315 degrees to the blow-off hole of the outer pipe 103. In this way, the gas on the space between the inner pipe 120 and the outer pipe 103 is uniformized, and the uniformization of the deposited film thickness and film quality in the circumferential direction of a circular pipe-shaped supporting body 102 can be attained.

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 formed on a support by a plasma CVD method, in particular, a semiconductor such as an electrophotographic photosensitive member, a photovoltaic device, an image input line sensor, an imaging device, and a TFT. The present invention relates to a method and an apparatus for forming a deposited film capable of continuously forming a crystalline or non-single-crystalline semiconductor which can be suitably used as an element.

[0002]

2. Description of the Related Art Conventionally, amorphous silicon such as hydrogen has been used as an element member for semiconductor devices, electrophotographic photoreceptors, image input line sensors, imaging devices, photovoltaic devices, other various electronic elements, optical elements, and the like. Or / and amorphous silicon compensated with halogen (eg, fluorine, chlorine, etc.)
A-Si (H, X)], or non-monocrystalline deposited films or crystalline deposited films such as diamond films and polysilicon films. It has been put to practical use. And such a deposited film is plasma C
VD method, that is, formed by a method of decomposing a raw material gas by direct current or high frequency, or glow discharge by microwave and forming a deposited film on a support such as glass, quartz, heat-resistant synthetic resin film, stainless steel, and aluminum, Various devices have been proposed for this purpose.

For example, FIG. 2 shows a plasma CVD method (hereinafter, referred to as a plasma CVD method).
FIG. 2 is a schematic configuration diagram illustrating an example of an apparatus for manufacturing an electrophotographic photosensitive member by PCVD). The configuration of the manufacturing apparatus shown in FIG. 2 is as follows. This apparatus is roughly divided into a deposited film forming apparatus 200, a source gas supply apparatus (not shown), and exhaust apparatuses 214 and 215 for reducing the pressure inside the cylindrical reaction vessel 201. Film forming apparatus 20
In the cylindrical reaction vessel 210 in FIG.
2. Heater 209 for heating the support, raw material gas introduction pipe 20
4 and a high-frequency matching box 211
Is connected.

[0004] A source gas supply device (not shown) is made of SiH ₄ , Ge.
It consists of a source gas cylinder (not shown) such as H ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH ₃ , a valve (not shown) and a mass flow controller (not shown).
It is connected to a gas introduction pipe 204 in the cylindrical reaction vessel 201 via (not shown).

The formation of a deposited film using such a conventional deposited film forming apparatus is performed, for example, as follows. First,
The cylindrical support 202 is set in the cylindrical reaction vessel 201, and the inside of the cylindrical reaction vessel 201 is evacuated by the exhaust device 214. Subsequently, the temperature of the cylindrical support 202 is controlled to a predetermined temperature of 20 to 450 ° C. by the support heating heater 209. In order to allow the source gas for forming the deposited film to flow into the cylindrical reaction vessel 201, it is confirmed that the valve of the gas cylinder (not shown) and the leak valve 212 of the cylindrical reaction vessel are closed, and the inflow valve ( (Not shown), the outflow valve (not shown), and the auxiliary valve (not shown) are confirmed to be open. First, the main exhaust valve 213 is opened to exhaust the inside 201 of the cylindrical reaction vessel and the gas distribution pipe 203. .

Next, the reading of the vacuum gauge 217 is about 6.7 × 1.
When the ^pressure becomes 0 ^-4 Pa, the auxiliary valve (not shown) and the outflow valve (not shown) are closed. After that, open each valve (not shown) from the gas cylinder (not shown) and introduce each gas.
(Not shown), each gas pressure is adjusted to ² kg / cm ² .
Next, the inflow valve (not shown) is gradually opened, and each gas is introduced into the mass flow controller (not shown).

After the preparation for film formation is completed as described above, each layer is formed in the following procedure. Cylindrical support 20
When the temperature of 2 reaches a predetermined temperature, an outflow valve (not shown)
The necessary ones and an auxiliary valve (not shown) are gradually opened, and a predetermined gas is introduced from a gas cylinder (not shown) into the cylindrical reaction vessel 201 through a gas distribution pipe 203.
Next, each raw material gas is adjusted to a predetermined flow rate by a mass flow controller (not shown). At this time, the opening of the main valve 218 is adjusted while watching the vacuum gauge 217 so that the pressure in the cylindrical reaction vessel 201 becomes a predetermined pressure of 133 Pa or less.

When the internal pressure becomes stable, the frequency becomes 13.5.
A 6 MHz high frequency power supply (not shown) is set to a desired power, and high frequency power is introduced into the cylindrical reaction vessel 201 through the high frequency matching box 211 to generate glow discharge. 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 202.

After the desired film thickness is formed, 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 the outflow valves other than the necessary gas are closed, and each gas flows into the cylindrical reaction vessel 201 from the outflow valve (not shown). To avoid remaining in the piping leading to the reaction vessel 201, the outflow valve (not shown) is closed, the auxiliary valve (not shown) is opened, the main exhaust valve 213 is fully opened, and the system is once evacuated to high vacuum. Perform the exhausting operation as needed.

[0010] When a deposited film having a large area such as an electrophotographic photosensitive member is formed in this manner, it is necessary to make the film thickness and film quality uniform, and various device configurations have been proposed. For example, according to Japanese Patent Application Laid-Open No. 4-247877, in a microwave plasma CVD deposited film forming apparatus, a source gas introduction pipe is configured as a multi-car pipe, and the number of gas discharge holes provided in the multi-pipe is reduced by the A technique has been disclosed in which the gas distribution in the reaction vessel is made uniform by increasing the temperature from the inside to the outside.

According to JP-A-58-30125,
For the introduction of the raw material gas, a gas pipe for gas introduction independent of the cylindrical electrode is used, and the cross-sectional area and interval of the gas discharge holes provided in the gas pipe are changed in the longitudinal direction of the cylindrical support, so that the raw material gas is supplied. A technique for improving the film thickness and film quality by uniformly discharging the film is disclosed. Also, Japanese Patent Application Laid-Open No. 58-32413
According to the publication, even in the cylindrical electrode serving also as the gas introduction means, even when the gas pipe for gas introduction is used, by setting the direction of the gas discharge holes so that the raw material gas rotates in a fixed direction, A technique for improving the uniformity of film thickness and film quality is disclosed.

According to Japanese Patent Application Laid-Open No. 62-218573, there is a technique for improving the uniformity of the film thickness and film quality without rotating the support by connecting the upper and lower portions of the gas introduction pipe with a branch pipe. It has been disclosed. Also, JP-A-63
According to Japanese Patent No. 479, the support is rotated by defining the relationship between the angle between the gas discharge hole of the gas inlet tube and the cylindrical support, the inner diameter of the cylindrical electrode, and the inner diameter of the cylindrical support. There is disclosed a technique for improving the uniformity of the film thickness and film quality without performing the method.

According to Japanese Patent Application Laid-Open No. 63-7373, a cylindrical support is rotated by using a gas inlet pipe and defining the relationship between the cross-sectional area of the gas inlet pipe and the cross-sectional area and number of the gas discharge holes. A technique for making the thickness and quality of a deposited film uniform without performing the method is disclosed. Also, Japanese Patent Application Laid-Open No. 9-36
According to Japanese Patent Publication No. 52, with respect to the longitudinal direction of the cylindrical support,
A technique has been disclosed in which a material gas introduction pipe is inclined using a ceramic ring to make the characteristic unevenness in the longitudinal direction uniform. These techniques have improved the uniformity of the film thickness and film quality of the electrophotographic photoreceptor, and accordingly the yield has been improved.

[0014]

However, the photoreceptor for electrophotography manufactured by a conventional film forming apparatus has been made uniform in film thickness, film quality, etc., and has been improved in the yield. In fact, there is room for further improvement in achieving improvement. In particular, high image quality, high speed, and high durability of electrophotographic devices are rapidly progressing, and in electrophotographic photoreceptors, charging performance and sensitivity are maintained while further improving electrical and photoconductive characteristics. On the other hand, it is required to greatly extend the performance under any environment.

Under these circumstances, the above-mentioned prior art 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 is still not sufficient.
In particular, it is necessary to obtain a more uniform film as an issue of further improving the image quality of the amorphous silicon-based photoconductor. For that purpose, it is necessary to balance the flow rate and velocity of the gas in the reaction space.

An object of the present invention is to solve the above-mentioned problems in a method and an apparatus for forming a deposited film used in an electrophotographic photoreceptor by overcoming the above-mentioned problems in the conventional deposited film forming apparatus. It is another object of the present invention to satisfy the above requirements. That is, on the main day of the present invention, the plasma CV capable of constantly forming a deposited film having a uniform thickness and quality by balancing the amount of gas in the reaction vessel.
An object of the present invention is to provide a method and an apparatus for forming a deposited film by a method D. Another object of the present invention is to improve various physical properties of a film to be formed, a film forming speed, reproducibility, improve film productivity, and dramatically improve the yield in mass production. An object of the present invention is to provide an apparatus for mass-producing a deposited film by a plasma CVD method.

[0017]

Means for Solving the Problems The present inventors have made intensive studies to overcome the above-mentioned problems in the conventional method of forming a deposited film and achieve the above-mentioned object of the present invention. The source gas introduction pipe has a gas distribution pipe for supplying the source gas from the source gas supply source, and the source gas distribution pipe has at least a double pipe configuration, and the source gas is introduced into the inner pipe of the double pipe. It has been found that the effect of this on the uniformity of the deposited film greatly.

That is, according to the present invention, the gas distribution pipe has a double pipe structure, and a raw material gas introduced from a raw gas supply source is introduced into an inner pipe of the double pipe, and a gas blowing hole of the inner pipe is provided. Through a gas discharge hole of a gas introduction pipe connected to the outer pipe of the double pipe through the gas pipe, to make the gas balance discharged into the reaction space uniform in the circumferential direction of the cylindrical reaction vessel. By providing the gas discharge holes of the inner pipe of the heavy pipe at 45 degrees or more and 315 degrees or less with respect to the gas discharge holes provided in the outer pipe, gas is released at an appropriate position. By uniformizing the gas in the circumferential direction before being released from the outer tube in the space with the outer tube, uniformization of the deposited film thickness and film quality in the circumferential direction of the cylindrical support is achieved. By having two or more gas blowing holes in the inner pipe of the double pipe It is intended to equalize the gas balance in the cylindrical reaction vessel circumferential direction.

[0019]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1A is a cross-sectional view schematically showing the arrangement of a counter electrode including a cylindrical reaction vessel serving as a source gas introduction tube and an electrode, and a cylindrical support in a deposition film forming apparatus using a plasma CVD method of the present invention. is there. FIG. 1A shows a deposition film forming apparatus 100, a cylindrical reaction vessel 101 also serving as an electrode, a cylindrical support 102, a double pipe 103 as a source gas distribution pipe, a gas pipe 104,
FIG. 1B shows an exhaust pipe, and FIGS. 1B to 1D are detailed cross-sectional views schematically showing a double pipe which is a source gas distribution pipe in the present invention, and FIG. FIG. 3C is a vertical cross-sectional view of the outer pipe and the gas introduction pipe, FIG. 3C is a top cross-sectional view of the double pipe, and FIG.

In the conventional method and apparatus for forming a deposited film, the raw material gas is introduced from the lower portion of the gas introduction pipe. However, since the gas supply source has a single pipe structure and a single gas supply source, the gas balance is not uniform in the circumferential direction. Becomes Therefore, when the raw material gas is distributed in several places in the circumferential direction of the cylindrical reaction vessel, the amount of the raw material gas supplied to the introduction gas pipe decreases as the distance from the supply port of the raw material gas supply source decreases, and And the gas balance becomes uneven, causing unevenness of the deposited film thickness or film quality in the circumferential direction of the cylindrical reaction vessel.

In the present invention, the source gas distribution pipe has at least a double pipe configuration, a source gas supply source is connected to the inner pipe of the double pipe, and the source gas is introduced into the inner pipe of the double pipe. By doing so, the gas balance of the amount of gas discharged into the reaction space through the gas discharge hole of the gas introduction pipe connected to the outer pipe of the double pipe can be made uniform in the circumferential direction of the cylindrical reaction vessel. did it. It is preferable that the gas discharge holes provided in the inner pipe of the double pipe are designed so that the gas is not directly blown into the raw material gas introduction pipe connected to the outer pipe of the double pipe. By setting the gas discharge hole of the inner tube of the tube to 45 degrees to 315 degrees with respect to the gas discharge hole of the outer tube, gas is released in the circumferential direction before being released from the outer tube due to the gap between the inner tube and the outer tube. As a result, the deposited film thickness and film quality in the circumferential direction of the cylindrical support were made uniform.

The gas discharge hole of the inner pipe of the double pipe is
By providing at least two or more, the balance of the gas amount in the reaction space was made more appropriate, and the quality and thickness of the deposited film to be deposited could be made uniform in the circumferential direction of the cylindrical support. . In addition, the same effect was obtained in the case of a triple pipe for the source gas distribution pipe.

The support used in the present invention may be conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au, In, N
Examples include metals such as b, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof, for example, stainless steel.

Further, at least the light-receiving layer of an electrically insulating support such as a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene and polyamide, glass and ceramic is formed. A support having a surface on the side to be conductive-treated can also be used.

The support used in the present invention may be in the form of a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface, and the thickness of the support is such that a desired electrophotographic photosensitive member can be formed. It is appropriately determined so as to obtain, but when flexibility as an electrophotographic photoreceptor is required, it can be as low as possible as long as the function as a support can be sufficiently exhibited. However, the support is usually 10 μm in view of production, handling, mechanical strength and the like.
That is all.

In particular, in the case of performing image recording using coherent light such as laser light, in order to more effectively eliminate image defects caused by so-called interference fringe patterns appearing in a visible image, the surface of the support is preferably used. Irregularities may be provided. The unevenness provided on the surface of the support is described in JP-A-60-168156.
No. 60-178457 and No. 60-225854.

As another method for more effectively eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, a concave-convex shape formed by a plurality of spherical trace depressions is provided on the surface of a support. You may. That is, the surface of the support has irregularities finer than the resolution required for the electrophotographic photosensitive member, and the irregularities are caused by a plurality of spherical trace depressions. The unevenness due to the plurality of spherical trace depressions provided on the surface of the support is created by a known method described in JP-A-61-231561.

In order to form a deposited film by the glow discharge method using the apparatus of the present invention, basically, a silicon atom is formed.
A source gas for supplying Si capable of supplying (Si), and a hydrogen atom
A source gas for supplying H capable of supplying (H) and / or a source gas for supplying X capable of supplying a halogen atom (X) are introduced into a reaction vessel in a desired gas state, and Glow discharge is caused to occur, and a layer made of A-Si: (H, X) may be formed on a predetermined support previously set at a predetermined position.

The substances that can be used as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si.
₄ gaseous state of H _10, etc., or silicon hydride can be gasified
(Silanes) are mentioned as ones used for fabric effect, and SiH ₄ and Si ₂ H ₆ are mentioned as preferable ones in terms of ease of handling at the time of forming a layer and good Si supply efficiency. Then, hydrogen atoms are structurally introduced into the deposited film to be formed, and the control of the introduction ratio of hydrogen atoms is further facilitated. It is necessary to form a layer by further mixing a desired amount of a gas of a silicon compound containing H ₂ and / or He or a hydrogen atom with the above gas.

Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio. Also useful as a source gas for supplying halogen atoms used in the present invention are gaseous or gasizable halogen compounds such as halogen gas, halides, halogen-containing interhalogen compounds, and halogen-substituted silane derivatives. Are preferred. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound.

As the halogen compound which can be suitably used in the present invention, specifically, fluorine gas (F ₂ ), BrF, Cl
Examples of the compound include halogen compounds such as F, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ . As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, silicon fluoride such as SiF ₄ or Si ₂ F ₆ is preferable.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the deposited film, for example, the temperature of the support, the amount of the raw material used to contain hydrogen atoms and / or logene atoms, and the like can be controlled. What is necessary is just to control the amount introduced into the reaction vessel, the discharge power and the like.

In the present invention, the deposited film preferably contains atoms for controlling conductivity as necessary.
The atoms controlling the conductivity may be contained in the deposited film in a uniformly distributed state, or may be present in the layer thickness direction in a non-uniform distribution state. . Examples of the atom that controls the conductivity include so-called impurities in the semiconductor field, and an atom belonging to Group IIIb of the periodic table that gives p-type conductivity (hereinafter, referred to as an atom).
An abbreviated group IIIb atom which gives n-type conductivity can be used.

Examples of the group Шb atom include, specifically,
There are boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. Specific examples of group Vb atoms include phosphorus.
(P), arsenic (As), antimony (Sb), bismuth (Bi) and the like, and P and As are particularly preferable. The content of the atoms controlling the conductivity incorporated in the deposited film is preferably 1 × 10
⁻² to 1 × 10 ⁴ atomic ppm, more preferably 5 × 10 ⁻²
~ 5 × 10 ³ atomic ppm, optimally 1 × 10 ^-1 to 1 × l
0 ³ desirably are atomic ppm.

Atoms for controlling conductivity, for example, IIIb
To structurally introduce a group V atom or a group Vb atom,
In forming the layer, a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom 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, those which are gaseous at ordinary temperature and normal pressure or those which can be easily gasified at least under layer forming conditions are employed. Is desirable.

As such a raw material for introducing a Group IIIb atom, there is a symbiotic relationship.
_{2 H 6, B 4 H 10} , B 5 H 9, B 5 H 11, B 6 H 10, B 6 H 12, B 6 6
Examples thereof include boron hydride such as H ₁₄ and halogenated ligands such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , G
a (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like can also be mentioned.

Effective as a raw material for introducing group Vb atoms
Is used for introducing a phosphorus atom._Three, P_Two
H_FourPhosphorus hydride, PH_FourI, PF_Three, PF_Five, PCl_Three, PC
l_Five, PBr_Three, PBr_Five, PI_ThreeAnd the like.
You. In addition, AsH_Three, AsF_Three, AsCl_Three, AsBr_Three, AsF_Five,
SbH_Three, SbF_Three, SbF_Five, SbCl _Three, SbCl_Five, BiH_Three, BiCl
_Three, BiBr_ThreeAre also effective starting materials for introducing group Vb atoms.
Can be listed as Also, these conductive
If necessary, the raw material for atom introduction controlling H_TwoYou
And / or diluted with He.

In order to achieve the object of the present invention and to form a deposited film having desired film characteristics, the mixing ratio of the gas for supplying Si and the diluent 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 H ₂ and / or He used as a dilution gas is properly selected within an optimum range in accordance with the layer design, the H ₂ and / or He to the Si-feeding gas, usually 1 to 2
It is desirable to control to a range of 0 times, preferably 2 to 15 times, and optimally 3 to 10 times.

Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected according to the layer design.
10 ^{−2 to} 1330 Pa, preferably 6.7 × 10 ^{−2 to} 6
The pressure is preferably 70 Pa, most preferably 1 × 10 ^{−1 to} 133 Pa. Similarly, the optimum range of the discharge power is also appropriately selected according to the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 0.1 to 7 times, preferably 0.5 to 6 times. Optimally, it should be set in the range of 0.7 to 5 times. Further, the temperature of the support is appropriately selected in an optimum range according to the layer design.
The temperature is desirably set to 00 to 350 ° C.

In the present invention, the preferable ranges of the temperature of the support and the gas pressure for forming the deposited film include the above-mentioned ranges. However, these conditions are not usually determined separately and independently. It is desirable to determine the optimum value based on mutual and organic relevance in order to form an electrophotographic photoreceptor having desired characteristics.

[0041]

EXAMPLES Hereinafter, the deposited film forming apparatus of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[Example 1] Length 358 mm, outer diameter φ108
mm mirror-finished Al cylinder (using an Al holder (length: 500 mm) on which a cylindrical support is placed) and using the apparatus shown in FIG.
A light receiving layer composed of a photosensitive layer and a surface layer was formed under the manufacturing conditions shown in Table 1. In this example, a double pipe as a source gas distribution pipe was configured as shown in FIGS. 1 (a) to 1 (d).
As for the gas discharge holes provided in the inner pipe of the double pipe which is the raw material gas distribution pipe, two gas discharge holes having a shape which blows out in a position direction symmetric to the discharge holes of the outer pipe are provided and connected to the outer pipe. 10 gas introduction pipes are arranged in a line in the circumferential direction and 20 in the longitudinal direction.
The gas blowing direction was the direction of the cylindrical reaction vessel.

[Comparative Example 1] A sample was manufactured under the same conditions as in Example 1 except that the source gas distribution pipe had a single pipe structure.

[0044]

[Table 1] With respect to the electrophotographic photoconductors manufactured in Example 1 and Comparative Example 1, unevenness in the film thickness circumferential direction and unevenness in the charging potential circumferential direction were evaluated by the following evaluation methods. Table 2 shows the results. (Film thickness circumferential direction unevenness) Along the circumferential direction of the electrophotographic photosensitive member,
The film thickness of the deposited film was measured, and when the variation from the average value of the film thickness was within 5%, it was evaluated as “◎”.
A four-point evaluation was performed in which 0% or less was evaluated as "△" and 10% or more was evaluated as "x". (Charge potential circumferential direction unevenness) Electrophotographic device (Canon NP6
The electrophotographic photosensitive member prepared in (Modification 150 for test) was set, and the charging potential was measured in the circumferential direction of the electrophotographic photosensitive member. “の も の” indicates that the variation of the charged potential from the average potential was within 5%, “、” indicates that the variation was within 8%, and “△” indicates that the variation was within 10%. A four-point evaluation was performed.

[0045]

[Table 2] As is apparent from Table 2, good results were obtained with respect to unevenness in the circumferential direction by using a double pipe for the raw material gas distribution pipe.

Example 2 Length 358 mm, outer diameter φ108
Using an Al holder (length 500 mm) on which an Al cylinder (cylindrical support) with a mirror finish of
A charge injection blocking layer on the support using the device shown in FIG.
A light receiving layer composed of a photosensitive layer and a surface layer was formed under the manufacturing conditions shown in Table 1. In this example, a double pipe as a source gas distribution pipe was configured as shown in FIGS. 1 (a) to 1 (d).

The direction of the gas discharge holes provided in the inner pipe of the double pipe as the raw material gas introduction pipe was changed inside the inner pipe.
The electrophotographic photosensitive member produced in Example 2 was evaluated for unevenness in the film thickness circumferential direction and unevenness in the charging potential circumferential direction by the same evaluation method as in Example 1. Table 3 shows the results together with Comparative Example 1.

[0048]

[Table 3] * The same direction as the direction of the outer gas introduction tube is set to 0 degree. However, the gas is not directly blown into the gas inlet pipe of the outer pipe. As is evident from Table 3, a good result is obtained with respect to the unevenness in the circumferential direction by using the source gas introduction pipe as a double pipe, and the direction of the discharge hole of the inner pipe is set to 45 degrees with respect to the outer pipe.
By setting the angle to not less than 315 degrees, good results were further obtained for unevenness in the circumferential direction.

[Embodiment 3] Length 358 mm, outer diameter φ108
Using an Al holder (length 500 mm) on which an Al cylinder (cylindrical support) with a mirror finish of
A charge injection blocking layer on the support using the device shown in FIG.
A light receiving layer composed of a photosensitive layer and a surface layer was formed under the conditions shown in Table 1. In this example, a double pipe as a source gas distribution pipe was configured as shown in FIGS. 1 (a) to 1 (d).

The gas discharge holes provided in the inner tube of the double tube which is the raw material gas introduction tube are installed in a shape which blows out inside the inner tube in a direction symmetric to the discharge holes of the outer tube, and the number thereof is one. Was changed from eight to eight. The gas inlet pipe connected to the outer pipe
Ten were arranged in the circumferential direction and 20 were arranged in the longitudinal direction, and the gas blowing direction was the cylindrical reaction vessel direction. Regarding the electrophotographic photoreceptor produced in Example 3, the film thickness was uneven in the circumferential direction.
The unevenness in the circumferential direction of the charged potential was evaluated by the same evaluation method as in Example 1. The results are shown in Table 4 together with Comparative Example 1.

[0051]

[Table 4] As is evident from Table 4, good results were obtained with respect to circumferential unevenness by using at least two or more gas discharge holes in the double pipe of the raw material gas distribution pipe.

Example 4 A charge injection blocking layer, a charge transport layer, a charge generation layer, and a charge injection layer were formed on the support in the same manner as in Example 1 except that the film forming conditions were prepared as shown in Table 5. When a light receiving layer composed of a surface layer was produced, good results were obtained as in Example 1.

[0053]

[Table 5] Example 5 A light receiving layer comprising a charge injection blocking layer, a photosensitive layer, and a surface layer on the support in the same manner as in Example 1 except that the film forming conditions shown in Table 6 were used in the VHF-PCVD method. As a result, as in Example 1, good results were obtained.

[0054]

[Table 6] Example 6 A light receiving layer composed of a charge injection blocking layer, a photosensitive layer, and a surface layer was formed on the support in the same manner as in Example 1 except that the gas distribution pipe was a triple pipe.

[0055]

[Table 7] As is clear from Table 7, good results were obtained with respect to unevenness in the circumferential direction even when the source gas distribution pipe was a triple pipe.

[0056]

According to the present invention, a gas distribution pipe for supplying a raw material gas from a raw gas supply source is provided in a plurality of raw gas introduction pipes, and the distribution pipe has at least a double pipe configuration. By connecting to the source gas supply source, the gas balance discharged into the reaction space through the gas discharge holes provided in the outer tube of the double tube, uniform in the circumferential direction of the cylindrical reaction vessel, Provided is a method and an apparatus for forming a deposited film by a plasma CVD method in which a deposited film thickness and film quality in a circumferential direction of a cylindrical support are made uniform, and a deposited film having a uniform film thickness and film quality can be constantly formed. .

The gas flow in the reaction vessel is stabilized, a deposited film having a uniform film thickness and film quality is constantly formed, image defects are drastically reduced, mass production becomes possible, and the deposition yield is drastically improved. A film forming method and a film forming apparatus are provided, and even when mass-producing an electrophotographic photoreceptor, a remarkable effect such as a remarkable improvement in yield can be achieved.

[Brief description of the drawings]

FIG. 1 shows a cylindrical reaction vessel also serving as an electrode in a method and an apparatus for forming a deposited film by a plasma CVD method of the present invention.
FIG. 2 is a schematic explanatory view showing a cylindrical support and a double pipe which is a source gas distribution pipe.

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

[Explanation of symbols]

100, 200 Deposition film forming apparatus 101, 201 Cylindrical reaction vessel 102, 202 (also serving as electrode) Cylindrical support 103, 203 Source gas distribution pipe (outer pipe of double pipe) 104, 204 Source gas introduction pipe 105,205 Exhaust pipe 109 Heater for supporting body heating 111,211 Matching box 112,212 Leak valve for reaction vessel 113,213 Main exhaust valve 114,214 Mechanical booster pump 115,215 Rotary pump 116,216 Source gas introduction valve 117,217 Vacuum meter 120 Inner tube

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroyuki Katagiri 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yoshio Segi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon In-house F term (reference) 4K030 AA05 AA06 AA07 EA05 LA12 LA17 5F045 AA08 AB04 AC01 AC02 AC08 AC17 AC18 AC19 AD06 AD07 AE11 AE13 AE15 AE17 AE19 AE21 AE23 BB01 CA13 CA15 CA16 DA52 EC02 EE04 EE12

Claims (6)

[Claims] A cylindrical support is disposed on a cylindrical support holding means in a cylindrical reaction vessel of a film forming apparatus by a plasma CVD method, and is disposed on a coaxial outer periphery of the support in a longitudinal direction of the support. A source gas for film formation was introduced into the cylindrical reaction vessel through a plurality of source gas introduction pipes provided along the same, discharge energy was introduced into the reaction vessel, and introduced into the reaction vessel. In the deposited film forming method of forming a deposited film on the surface of the cylindrical support by exciting the source gas for film formation and supplying a source gas from a source gas supply source to the plurality of source gas introduction pipes, A method for forming a deposited film, the method comprising: providing a gas distribution pipe for performing the gas distribution, forming the distribution pipe at least in a double pipe configuration, and connecting an inner pipe of the double pipe to a source gas supply source. 2. The method according to claim 1, wherein the angle of the gas discharge hole provided in the inner pipe of the double pipe is within a range of 45 to 315 degrees with respect to the gas discharge hole provided in the outer pipe of the double pipe. The method for forming a deposited film according to claim 1, wherein: 3. The method according to claim 1, wherein at least two or more gas discharge holes are provided in the inner tube of the double tube. 4. A cylindrical support is disposed on a cylindrical support holding means in a cylindrical reaction vessel of a film forming apparatus by a plasma CVD method, and is disposed on a coaxial outer periphery of the support in a longitudinal direction of the support. A source gas for film formation was introduced into the cylindrical reaction vessel through a plurality of source gas introduction pipes provided along the same, discharge energy was introduced into the reaction vessel, and introduced into the reaction vessel. In a deposition film forming apparatus for forming a deposition film on the surface of the cylindrical support by exciting and seeding the film forming source gas, a source gas from a source gas supply source is supplied to the plurality of source gas introduction pipes. A gas distribution pipe for performing deposition, wherein the distribution pipe has at least a double pipe configuration, and an inner pipe of the double pipe is connected to a source gas supply source. 5. The gas discharge hole provided in the inner pipe of the double pipe is set in a range of 45 to 315 degrees with respect to the gas discharge hole provided in the outer pipe of the double pipe. The deposition film forming apparatus according to claim 4, characterized in that: 6. The deposition film forming apparatus according to claim 4, wherein the inner pipe of the double pipe has at least two or more gas discharge holes.