JP2001323375A - Method and apparatus for forming a deposited film by plasma CVD - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cylindrical electrode constituting a vacuum chamber and a cylindrical support serving as a counter electrode in the center of the vacuum chamber, and to feed raw material through a plurality of holes provided in the cylindrical electrode. In a film forming apparatus based on a plasma CVD method for releasing a gas and forming a deposited film on the cylindrical support, a deposited film having a uniform film thickness and film quality is constantly maintained by stabilizing a gas flow in a reaction vessel. Provided are a method and an apparatus capable of dramatically reducing image defects, and dramatically improving the yield by mass production. SOLUTION: A deposited film having a plurality of tubular cavities separately provided along a longitudinal direction inside the cylindrical electrode for supplying a fluid for cooling the cylindrical electrode and the source gas. And a method of manufacturing a deposited film using the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plasma CVD method.
By (PCVD), a functional deposited film on a support, particularly a photoconductor for electrophotography, a photovoltaic device, a line sensor for image input, an imaging device, a crystalline material, which can be suitably used as a semiconductor element such as a TFT, or The present invention relates to a method and an apparatus for forming a deposited film for continuously forming a non-single-crystal semiconductor.

[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 by hydrogen or / and halogen (eg, fluorine, chlorine, etc.) [hereinafter A-Si
(Abbreviated as (H, X)) or a crystalline deposited film such as a diamond thin film.
Some of them have been put to practical use. Then, such a deposited film is decomposed by a plasma CVD method, that is, a raw material gas is decomposed by a glow discharge by direct current, high frequency, or microwave, and deposited on a support such as glass, quartz, a heat-resistant synthetic resin film, stainless steel, or aluminum. The film is formed by a method of forming a film, and various apparatuses for that purpose have been proposed.

For example, FIG. 6 is a schematic diagram showing an example of an apparatus for manufacturing a photoconductor for electrophotography by high-frequency plasma CVD, and FIG. 7 is a schematic diagram showing a cylindrical electrode constituting a vacuum chamber. FIG.

This apparatus is roughly composed of a deposition apparatus, a source gas supply apparatus, and an exhaust apparatus for reducing the pressure inside the cylindrical electrode (201). A cylindrical support (202), a heater for heating the support (205) are installed in the cylindrical electrode (201) in the deposition apparatus, and a raw material gas discharge hole (204) in an inner wall (204) of the cylindrical electrode (201). 209), and a high frequency matching box (not shown) is connected to the introduction portion (206) of the outer wall of the cylindrical electrode. 207 denotes an upper insulator, 208 denotes a lower insulator, and 210 denotes an exhaust line.

[0005] The raw material gas supply device is composed of SiH ₄ , GeH ₄ , H ₂ ,
It is composed of a cylinder of raw material gas such as CH ₄ , B ₂ H ₆ , PH ₃ , an outflow valve, a mass flow controller, and an auxiliary valve in this order.

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 electrode (201), and the inside of the cylindrical electrode (201) is evacuated by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the temperature of the cylindrical support (202) is set to 20 by the support heating heater (205).
The temperature is controlled to a predetermined temperature in the range of 450C to 450C.

When the temperature of the cylindrical support (202) reaches a predetermined temperature, a source gas is introduced from a source gas supply device into a hollow portion of the cylindrical electrode (201) through a source gas supply pipe (203). Gas is released into the cylindrical electrode (201) from a gas discharge hole (209) provided in the inner wall (204) of the cylindrical electrode. Next, each source gas is adjusted by a mass flow controller so as to have a predetermined flow rate. At that time, the cylindrical electrode (20
1) Adjust the opening amount of the main valve provided in the exhaust line while watching the vacuum gauge so that the internal pressure becomes a predetermined pressure of 133 Pa or less.

When the internal pressure becomes stable, the frequency 13.56
A high-frequency power source of MHz is set to a desired power, and a high-frequency power is introduced from an introduction portion (206) provided on the outer wall of the cylindrical electrode (201) through a high-frequency matching box to generate glow discharge. The raw material gas introduced into the cylindrical electrode (201) is decomposed by this discharge energy,
A deposition film mainly containing predetermined silicon is formed on the cylindrical support (202). 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 reactor, 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 that each gas is supplied to the cylindrical electrode (201).
Close the outflow valve, open the auxiliary valve, and fully open the exhaust main valve in order to avoid remaining in the piping from the outflow valve to the cylindrical electrode (201). Operation is performed as needed.

When a deposited film having a large area such as an electrophotographic photoreceptor is formed in this way, 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. 59-38375, a cylindrical chamber constituting a vacuum chamber is formed in a double structure, a gas chamber is provided in the electrode, and further provided on the inner wall of the cylindrical electrode. A technique is disclosed in which the source gas is uniformly discharged by adjusting the number of the plurality of gas discharge holes to make the film thickness uniform.

According to Japanese Patent Publication No. 4-38449, an external electrode plate forming a reaction chamber and an internal electrode plate having gas discharge holes are provided, and these two electrode plates have at least a cylindrical shape having the same potential. By adopting a dual structure device configuration,
A technique for improving the uniformity of film thickness and film quality is disclosed.

According to Japanese Patent Publication No. 5-32472, cylindrical first and second peripheral plates having large and small diameters are arranged concentrically in a reaction vessel, and the second peripheral plate is arranged on the second peripheral plate. A technique is disclosed in which gas is supplied uniformly by making the hole diameter of the provided passage hole smaller than the hole diameter of the first peripheral plate or increasing the number of holes.

[0015] These techniques have improved the uniformity of the film thickness and film quality of the electrophotographic photoreceptor, and accordingly the yield has been improved.

[0016]

However, the photoreceptor for electrophotography made by the conventional apparatus has been improved in the yield because the film thickness and the film quality have been made uniform, but in order to improve the overall characteristics. In fact, there is room for further improvement.

In particular, high image quality, high speed, and high durability of the electrophotographic apparatus are rapidly progressing. In the electrophotographic photoreceptor, the electric properties and photoconductive properties are further improved, and the charging ability and sensitivity are improved. There is a need to significantly extend performance in all environments while maintaining.

As a result of the improvement of the optical exposure device, the developing device, the transfer device, and the like in the electrophotographic apparatus in order to improve the image characteristics of the electrophotographic apparatus, the electrophotographic photosensitive member has a higher image characteristic than before. Improvement has been required.

Under these circumstances, the above-mentioned prior art has made it possible to make the film thickness and film quality uniform to some extent with respect to the above-mentioned problems, but it is still sufficient as a problem for further image quality. Absent. In particular, as issues for further improving the image quality of the amorphous silicon-based photoreceptor, it is necessary to obtain a uniform film and to suppress the occurrence 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 adhering to the inner wall of the cylindrical electrode during film formation scatters on the support, the deposited film grows abnormally, and a minute image defect occurs on an image. Therefore, it is necessary to prevent products such as a film attached to the support other than the support from scattering to the support.

An object of the present invention is to provide 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 an object of the present invention to solve the above problems and satisfy the above requirements.

That is, a main object of the present invention is to provide a plasma CVD method which balances the amount of gas in a reaction vessel, constantly forms a deposited film having a uniform thickness and quality, and can drastically reduce image defects. To provide a deposited film forming method and apparatus.

It is another object of the present invention to improve various physical properties of a film to be formed, a film forming speed, reproducibility, improve a film productivity, and dramatically improve a yield in mass production. It is an object of the present invention to provide an apparatus for mass-producing a deposited film by a plasma CVD method which enables the above.

[0023]

That is, the present invention provides a cylindrical electrode constituting at least a part of a side wall of a reaction chamber;
A vacuum-tightly sealed reaction space provided in the inner peripheral surface of the cylindrical electrode, a substrate holder for installing a cylindrical substrate for forming a deposited film in the reaction space, and a raw material in the reaction space. Source gas introducing means for introducing a gas, and high frequency energy introducing means for introducing high frequency energy for generating a glow discharge by exciting the source gas introduced into the reaction space using the cylindrical electrode. And an exhaust unit for exhausting the reaction space, wherein the side wall of the reaction chamber is
It has a plurality of cooling tubular cavities through which the cooling fluid of the cylindrical electrode flows, and a plurality of source gas tubular cavities for supplying a source gas to the source gas introducing means, and each of these tubular cavities is An apparatus for producing a deposited film, wherein the cylindrical electrode extends from the bottom to the head along the axial direction.

Further, a cylindrical substrate is set in a reaction space formed in the inner peripheral surface of a cylindrical electrode constituting at least a part of a side wall of the reaction chamber, and the reaction space is vacuum-tightly sealed to introduce a raw material gas. In a method for producing a deposited film by a plasma CVD method, comprising applying a high-frequency energy to excite the source gas to generate a glow discharge and form a deposited film on the cylindrical substrate, the method further comprises: A plurality of cooling tubular cavities through which the cooling fluid of the cylindrical electrode flows, and a plurality of raw material gas tubular cavities for supplying a raw material gas to the raw material gas introducing means are provided. A method of manufacturing a deposited film, comprising cooling a cylindrical electrode and supplying a source gas to the source gas introducing means.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a description will be given of the findings that have led to the present invention.

The present inventors have conducted intensive studies to overcome the above-mentioned problems in the conventional method for forming a deposited film and to achieve the above-mentioned object of the present invention. Inside, a plurality of tubular cavities as source gas introduction means along the longitudinal direction of the side wall, and introduction of a fluid (hereinafter referred to as a cooling fluid) for cooling an electrode along the longitudinal direction of the side wall. A plurality of tubular cavities as means, and the source gas is discharged through a plurality of holes provided in the side wall through the tubular cavity as the source gas introduction means, and The finding that flowing a fluid for cooling an electrode through a tubular cavity, which is a means for introducing a fluid, and forming a deposited film on the cylindrical support greatly affects the uniformity of the deposited film and the occurrence of image defects. I got

In the case of the conventional dual structure, the gas introduced from the tubular cavity as the gas introduction means has a large volume in the cavity provided between the outer wall and the inner wall having the double structure. However, it was difficult to supply the gas uniformly to the gas discharge holes provided on the outer wall. However, by adopting the apparatus configuration of the present invention, the gas introduced from the gas introduction pipe was formed into a double structure of the outer wall and the inner wall. Since the volume of the cavity provided between them is reduced, they are evenly distributed.

Further, by providing a circumferential distribution pipe and / or a longitudinal distribution pipe before introducing the gas into the cavity, the gas can be more uniformly distributed in the circumferential and longitudinal directions before the gas is supplied to the cavity. By doing so, gas release from the gas release holes provided on the outer wall becomes uniform. That is, the film quality and thickness of the deposited film can be made uniform in the circumferential direction or the longitudinal direction of the cylindrical support.

Further, depending on the type of the layer to be laminated on the cylindrical support, the gas amount, the internal pressure, the input power, etc. are different, so that it is particularly necessary to control the unevenness in the longitudinal direction. In the case of the dual structure, which is the conventional device configuration, since the cavity is an integrated type, the control of the longitudinal unevenness is performed by adjusting the distribution of the longitudinal gas discharge holes provided on the outer wall of the cylindrical electrode. However, in this case, since the distribution cannot be adjusted during the formation of the deposited film, unevenness occurs depending on the type of the layer to be laminated.

On the other hand, the device configuration of the present invention
Unlike the conventional double-structured integrated cavity, since a plurality of single gas are provided, the raw material gas is supplied by supplying a cavity according to a gas type for forming a deposited film or a layer configuration. Is possible.

That is, for the layer type to be laminated, only the cavity having gas distribution holes having an appropriate distribution is controlled by the source gas supply valve, or the source gas distribution pipe is connected by the layer type or the gas type. As a result, the gas balance of each layer type is made uniform in the longitudinal direction, and the film quality and film thickness of the deposited film are made uniform in the longitudinal direction of the cylindrical support. Things.

Further, in the present invention, the raw material gas is discharged from a plurality of holes provided in the cylindrical electrode through the tubular cavity as the raw material gas introduction passage, and the cooling fluid of the cylindrical electrode is discharged. By forming a deposited film on a cylindrical support by flowing it into a tubular cavity that is a flow channel, the film quality and thickness of the deposited film deposited as described above are made uniform, and the occurrence of image defects is suppressed. It is.

That is, in the case of the double structure of the conventional apparatus, the raw material gas released from the raw material gas discharge hole on the inner wall of the cylindrical electrode is immediately decomposed by plasma or temperature depending on the gas discharge hole on the inner wall of the cylindrical electrode. Therefore, a film is deposited on the end of the gas discharge hole on the inner wall of the cylindrical electrode. Due to the stress of the film during the formation of the deposited film for a long time, the deposited film is peeled off from the end of the gas discharge hole on the inner wall of the cylindrical electrode, and scatters in the form of a support. This is where image defects occur.

This phenomenon is related to the temperature of the portion where the film is deposited. When the temperature is high, the film grows, and when the temperature is low, it becomes polysilane. When polysilane is used, it does not accumulate at the end of the gas discharge hole on the inner wall of the cylindrical electrode, so that image defects are suppressed.

For this reason, in the conventional apparatus configuration, a method of cooling the cylindrical electrode is employed in order to prevent the temperature of the cylindrical electrode from being increased by the plasma or the heater for heating the support. If the cylindrical electrode has a double structure, a coiled pipe is provided on the outer wall of the cylindrical electrode,
Fluids such as water and liquid nitrogen flow through the pipe to cool the cylindrical electrode.However, it is indirect cooling, and the cylindrical electrode itself has a thick wall and poor heat conduction. Therefore, the vicinity of the gas discharge hole of the cylindrical electrode was not always sufficiently cooled.

The cooling of the cylindrical electrode is also performed in another device form, for example, Japanese Patent Publication No. 6-74.
Japanese Patent Publication No. 504 discloses a technique for cooling an electrode, although the gas introduction mode is different. However, in this case, the temperature is high near the gas introduction port, so that the film is easily peeled.

By adopting the apparatus configuration of the present invention, a plurality of tubular cavities as raw material gas introduction passages extending in the longitudinal direction of the cylindrical electrode and a gas provided in the inner wall of the cylindrical electrode in the longitudinal direction are provided. By providing a plurality of longitudinal cavities through which fluid for cooling along the vicinity of the discharge hole is provided, the cooling effect near the gas discharge hole is improved, and a film deposited at the end of the gas discharge hole Is removed, and as a result, the fine particles are scattered in the shape of a support, and the occurrence of minute image defects on an image caused by abnormal growth of the deposited film can be suppressed.

Further, since the cylindrical electrode is efficiently cooled, the film deposited on unnecessary portions is eliminated, the gas use efficiency is improved, and the film deposited on the support becomes a good quality film. As a result, an unexpected effect of improving the charging ability was obtained.

Further, in order to increase the cooling efficiency, the supply and discharge of the fluid to and from the tubular cavity, which is the flow path of the cooling fluid,
The fluid can be uniformly distributed in the circumferential direction by supplying and discharging the fluid through circumferential fluid distribution pipes provided above and below the tubular cavity that is the flow path of the fluid. This can eliminate cooling unevenness.

The supply of the fluid to the tubular cavity, which can be a fluid introduction pipe, is introduced from the lower side of the cylindrical electrode through a lower fluid distribution pipe, and is supplied through the upper fluid distribution pipe to the upper side of the cylindrical electrode. By discharging the fluid more, gravity is applied to the fluid, so that the fluid can be uniformly distributed in the circumferential direction, and uneven cooling of the cylindrical electrode can be eliminated. At this time, the supply and discharge ports of the fluid provided on the cylindrical electrode are not problematic at any position in the circumferential direction of the cylindrical electrode, but the cooling efficiency can be further increased by providing the fluid at the opposed position. It is.

Hereinafter, the present invention will be described in detail with reference to the drawings.

FIGS. 1 to 5 are cross-sectional views schematically showing the arrangement of a cylindrical electrode and a counter electrode including a cylindrical support in the apparatus for forming a deposited film by the plasma CVD method of the present invention. 1 and 2 are schematic sectional views of a deposited film forming apparatus, FIGS. 3 and 4 are schematic upper sectional views showing a cavity provided in a cylindrical electrode, and FIG. 5 shows a piping system. It is a schematic diagram.

In the figure, 101 is a cylindrical electrode, 102 is a counter electrode including a cylindrical support, 103 is a tubular cavity that can be a source gas introduction pipe, 104 is the inner wall of the cylindrical electrode, 105 is a heater for heating the support, 106 is a high-frequency introduction part of the outer wall of the cylindrical electrode, 107 is an upper insulator, 108 is a lower insulator, 109 is a gas discharge hole provided on the inner wall of the cylindrical electrode,
Reference numeral 110 denotes a lower peripheral gas distribution pipe in the cylindrical electrode, 111 denotes a peripheral gas distribution pipe in the cylindrical electrode inner part, 112 denotes a raw material gas inlet, 113 denotes an exhaust line, 114 denotes a longitudinal gas distribution pipe, and 115 denotes a circumferential direction. A gas distribution pipe, 116 is a tubular cavity which can be a fluid introduction pipe, 117 is a fluid introduction port, 120
Denotes a fluid discharge port, 118 denotes a fluid distribution pipe in the lower circumferential direction inside the cylindrical electrode, and 119 denotes a fluid distribution pipe in the upper circumferential direction of the cylindrical electrode.

In the present invention, the number of the plurality of tubular cavities which can be the source gas introduction pipe is preferably 4 or more and 100 or less, more preferably 10 or more and 60 or less. ing.

The diameter of a plurality of tubular cavities which can be used as a raw material gas introduction pipe is preferably 3 mm or more and 20 mm or less, more preferably 5 mm or more and 15 mm or less.

The plurality of tubular cavities which can be used as the source gas introduction pipe are arranged along the axial direction from the bottom to the head of the cylindrical electrode, and have a cross-sectional shape of the tubular cavity. Can be any of a circle, a square, and an ellipse, but a circle is suitable for the present invention in view of workability of the cavity.

Further, the plurality of tubular cavities that can be used as the source gas introduction pipes have a single pipe structure, but the same effect can be obtained even when at least a double pipe configuration is used.

In the case of the configuration as shown in FIG. 1, it is suitable for the present invention that the circumferential gas distribution pipe provided in the cylindrical electrode is provided at the top and bottom, but any one of them has no problem. There is no. Further, a gas distribution pipe in the longitudinal direction may be provided outside the cylindrical electrode, and the gas may be introduced from the raw material gas inlet (112) into the cavity through the gas distribution pipe in the longitudinal direction. In that case, it is preferable to distribute to at least one or more, and more preferably to distribute to two or more.

Further, it is preferable that the raw material gas inlet (112) is introduced from at least one or more,
More preferably, the introduction from two or more is suitable for the present invention.

In the configuration shown in FIG. 2, the circumferential gas distribution pipe (115) and the longitudinal direction distribution pipe (114) are provided outside the cylindrical electrode. Absent. Further, when a gas distribution pipe in the longitudinal direction is provided outside the cylindrical electrode, it is preferable that the gas is distributed to at least one or more, and more preferable that the gas is distributed to two or more.

Further, it is preferable that the raw material gas inlet (112) is introduced from at least one or more, more preferably from two or more.

The present invention is characterized in that a plurality of hollow portions which can serve as gas introduction pipes and a circumferential gas distribution pipe are provided in the cylindrical electrode. It is desirable to appropriately design the number of source gas inlets so as to obtain a desired deposited film.

FIG. 5 shows a piping system in which a plurality of tubular cavities serving as gas introduction channels and a plurality of tubular cavities serving as fluid introduction pipe channels are alternately arranged. Although suitable for the present invention, there is no problem with any arrangement as long as the effect of cooling the cylindrical electrode can be obtained, and it is desirable to appropriately design.

Also, like the plurality of tubular cavities which can be the source gas introduction pipe, the plurality of tubular cavities serving as the fluid introduction flow path extend along the axial direction from the bottom to the head of the cylindrical electrode. The cross-sectional shape of the tubular hollow portion can be any of a circular shape, a square shape, and an elliptical shape, but a circular shape is suitable for the present invention from the viewpoint of the workability of the hollow portion. .

Further, it is suitable for the present invention that the number of the plurality of tubular cavities serving as the fluid introduction passage is equal to the number of the plurality of tubular cavities serving as the gas introduction passage. However, as long as the effect of cooling the cylindrical electrode can be obtained, there is no problem with any number, and it is desirable to appropriately design.

Further, the diameter of the plurality of tubular cavities serving as the fluid introduction flow passages should be equal to the diameter of the plurality of tubular cavities serving as the gas introduction flow passages from the point of cavity processing. Although suitable for the present invention, there is no problem with any diameter as long as the effect of cooling the cylindrical electrode is obtained, and it is desirable to design as appropriate.

There is no problem with the fluid flowing through the plurality of tubular cavities, which are the fluid introduction flow paths, as long as a cooling effect can be obtained. However, water and liquid nitrogen are suitable for the present invention. ing.

FIGS. 8A and 8B are schematic views showing a piping system in the case where the above-mentioned hollow portions are switched and used, and FIG. 8A shows a tubular hollow portion serving as a gas introduction flow passage in a cylindrical electrode. The figure shows an example in which 18 tubular cavities, which are fluid introduction flow paths, are provided alternately, and 301 to 306, 311 to 311 in the figure.
16 is an automatic opening / closing valve, 307 is a circumferential gas distribution pipe 1,
308 is a circumferential gas distribution pipe 2, 309 is a source gas inlet 1, 310 is a source gas inlet 2, 317 is a fluid inlet,
Numeral 318 indicates a circumferential fluid distribution pipe.

FIG. 8 (a) shows the control of the gas introduction section into each cavity by automatic valve control.
(b) is controlled by the connection method of the circumferential gas distribution pipe. Since the gas discharge holes are appropriately arranged in the cavity in accordance with the type of the layer to be laminated, the deposited film thickness and the film quality can be made uniform.

FIG. 8 shows a specific example of gas introduction.
Using the apparatus configuration of (a), Si for forming a photoconductive layer which is an electrophotographic photoreceptor is provided at the source gas inlet 1 (309).
H ₄ and H ₂ gases are connected. Source gas inlet 2 (31
0) has a Si for laminating a surface layer on the photoconductive layer.
H ₄ , CH ₄ , and H ₂ gas are connected. First, the SiH ₄ and H ₂ gas introduced from the raw material gas inlet (309) are supplied to the circumferential gas distribution pipe (307) and the valves (301, 303, 30).
5) The photoconductive layer is introduced into the discharge space from the gas discharge holes via the cavity portions 17, 1, and 3 having gas discharge holes arranged appropriately for the film thickness and film quality unevenness of the photoconductive layer. Formed on a support. At this time, valves (302, 304, 3
06, 311 to 316) in the closed state, or in order to prevent blockage of the gas discharge holes provided in the hollow portion, through the raw material gas inlet 2 (310), the H ₂ gas as a diluent gas is introduced into the circumferential gas. Distribution pipe 2 (308), valve (312, 314,
316), the gas may be introduced into the minute amount discharge space from the gas discharge holes through the cavities 18, 2, and 4.

After the formation of the photoconductive layer, the raw material gas inlet (30
9), a valve upstream of the source gas inlet 2 (310)
(Not shown), the residual gas in the pipe is pulled up, and the valves (301 to 306, 311 to 316) are fully closed.

Thereafter, the SiH ₄ and CH ₄ gases introduced from the raw material gas inlet 2 (310) are supplied to the circumferential gas distribution pipe 2 (30).
8), gas (312, 314, 316), the thickness of the surface layer, and the gas discharge holes are introduced into the discharge space through the cavities 18, 2, and 4 having the gas discharge holes arranged so as to be suitable for uneven film quality. And a surface layer is formed on the cylindrical support. At this time, valves (311, 313, 315, 301 to 306)
Is closed or in order to prevent clogging of the gas discharge holes provided in the cavity, from the raw material gas inlet (309),
The H ₂ gas, which is a dilution gas, is supplied to the circumferential gas distribution pipe 1 (30
7), valves (301, 303, 306), cavity 17,
A small amount of gas may be introduced into the discharge space from the gas discharge holes via the first and third gas discharge holes.

After forming the surface layer, the raw material gas inlet 1 (30
9), a valve upstream of the source gas inlet 2 (310)
(Not shown), the residual gas in the pipe is pulled up, and the valves (301 to 306, 311 to 316) are fully closed. The gas is supplied to the other cavities in the same manner as in this example, but it is desirable to appropriately design the number of raw material gas inlets so as to obtain a desired deposited film.

As described above, by using the hollow portion by switching the layer type, the gas balance of each layer type is made uniform in the longitudinal direction, and the film quality and thickness of the deposited film to be deposited are cylindrically supported. It is intended to be uniform in the longitudinal direction of the body.

When the hollow portion of the present invention is used by switching between the layer type and the gas type, it is desirable to appropriately design the allocation of the hollow portion to each layer so as to obtain a desired deposited film.

In the case where an unused cavity is formed,
There is no problem with closing the valve or introducing the diluent gas.

The support used in the present invention may be either conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au, In, Nb, Te, V, Ti, Pt,
Examples include metals such as Pd and Fe, and alloys thereof, for example, stainless steel. 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 is cylindrical with a smooth surface or an uneven surface, and its thickness is appropriately determined so that a desired electrophotographic photosensitive member can be formed. When flexibility as a photographic photoreceptor is required, it can be made as thin as possible within a range where the function as a support can be sufficiently exhibited. However, the support is usually 10 μm or more in terms of production, handling, mechanical strength and the like.

In particular, when image recording is performed using coherent light such as laser light, unevenness on the surface of the support is required in order to more effectively eliminate image defects caused by so-called interference fringe patterns appearing in a visible image. May be provided. The irregularities provided on the surface of the support are described in JP-A-60-168156, JP-A-60-178457, and JP-A-60-22585.
It is prepared by a known method described in Japanese Patent Publication No.

As another method for more effectively eliminating image defects due to interference fringe patterns in the case of using coherent light of a laser beam, a concave-convex shape having a plurality of spherical trace depressions is provided on the surface of a support. Is also good. 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 irregularities due to the plurality of spherical trace depressions provided on the surface of the support are prepared 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 H supply capable of supplying (H) and / or a source gas for X supply capable of supplying a halogen atom (X) are introduced into a reaction vessel in a desired gas state, and are introduced into the reaction vessel. A glow discharge may be generated to form a layer of a-Si: H, X 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 preferably used, and SiH ₄ and Si ₂ H ₆ are more preferable in terms of easy handling at the time of forming the layer and high Si supply efficiency. Then, in order to structurally introduce hydrogen atoms into the deposited film to be formed, to control the introduction ratio of hydrogen atoms more easily, and to obtain a film characteristic that achieves the object of the present invention, It is necessary to form a layer by mixing a desired amount of a gas of H ₂ and / or He or a silicon compound containing a hydrogen atom. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

The raw material gas for supplying a halogen atom used in the present invention is, for example, a gaseous or gaseous gas such as a halogen gas, a halide, an interhalogen compound containing halogen, or a silane derivative substituted with halogen. The obtained halogen compounds 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. Specific examples of the halogen compound that can be suitably used in the present invention include fluorine gas (F ₂ ), BrF,
Examples thereof include interhalogen compounds such as ClF, 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 reaction of a raw material used to contain hydrogen atoms and / or halogen atoms, What is necessary is just to control the quantity introduced into a container, discharge power, etc.

In the present invention, it is preferable that the deposited film contains atoms for controlling conductivity as necessary.
The atoms for controlling the conductivity may be contained in the deposited film in a state of being distributed uniformly and uniformly, or there may be a part contained in the layer thickness direction in a non-uniform distribution state.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors.
An atom belonging to Group 13 of the periodic table that gives p-type conduction properties (hereinafter abbreviated as “group 13 atom”) or a member of Group 15 that gives n-type conduction properties (hereinafter “a Group 15 atom”)
Can be used.

As the Group 13 atom, specifically, 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 15 atoms include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like.
Particularly, P and As are preferable.

The content of atoms for controlling conductivity contained in the deposited film is preferably 1 × 10 ^-2 to 1 × 10 ^4.
Atom ppm, more preferably 5 × 10 ^{-2 to} 5 × 10 ³ atom p
pm, and most preferably 1 × 10 ⁻¹ to 1 × 10 ³ atom ppm.

In order to structurally introduce an atom for controlling conductivity, for example, a group 13 atom or a group 15 atom, a source material for introducing a group 13 atom or a first group
The raw material for introducing group V atoms is introduced into the reaction vessel in a gaseous state.
It may be introduced together with another gas for forming the deposited film. As a raw material for introducing a Group 13 atom or a raw material for introducing a Group 15 atom, a material which is gaseous at ordinary temperature and normal pressure or which can be easily gasified at least under layer forming conditions is employed. It is desirable.

As the raw material for introducing a group 13 atom, specifically, for introducing a boron atom, B ₂ H ₆ ,
Boron hydrides such as B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄ and boron halides such as BF ₃ , BCl ₃ , BBr ₃ No. In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ )
₃ , InCl ₃ , TlCl _{3 and the} like.

Effective as a starting material for introducing Group 15 atoms
Used for introducing phosphorus atoms is PH_Three, P_Two
H_FourSuch as hydrogenated phosphorus, PF_Three, PF_Five, PCl_Three, PCl_Five, PBr_Three,
PBr _Five, PI_Three, Etc., and PH_FourSuch as I
It is. 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 effective starting materials for introducing Group 15 atoms.
Can be listed as

Further, these raw materials for introducing atoms for controlling the conductivity may be diluted with H ₂ and / or He if necessary.

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.

H ₂ and / or H used as a diluent gas
The flow rate of e is appropriately selected in an optimum range according to the layer design. However, H ₂ and / or He is usually 1 to 20 times, preferably 2 to 15 times, optimally, Si supply gas. It is desirable to control to a range of 3 to 10 times.

Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected according to the layer design.
^{-2 to} 1300 Pa, preferably 6.7 × 10 ^{-2 to} 670 Pa, and most preferably 1 × 10 ^{-1 to} 133 Pa.

Similarly, the optimum range of the discharge power is appropriately selected according to the layer design. The discharge power with respect to the flow rate of the Si supply gas is usually 0.1 to 7 times, preferably 0.5 to 7 times. It is desirable to set the range to 6 times, optimally 0.7 to 5 times.

The optimum temperature of the support is appropriately selected according to the layer design.
It is desirable that the temperature be 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 photosensitive member having desired characteristics.

[0089]

The apparatus of the present invention will be described in more detail with reference to examples.

[Example 1] Length 358 mm, outer diameter φ108
Using an Al holder (length: 500 mm) on which an Al cylinder (cylindrical support) having a mirror-finished surface of 1.0 mm is mounted, the Al support is mounted on the support using the apparatus shown in FIG. 1 and the apparatus shown in FIG. A light receiving layer comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was formed under the manufacturing conditions shown in Table 1.

In this example, the tubular cavity as the raw material gas introduction passage and the tubular cavity as the fluid introduction passage in the cylindrical electrode are configured as shown in FIGS. 3, 4, and 5, respectively. The number of hollow portions was changed from 2 to 120. The inner diameter of the cavity was 5 mm, and the circumferential gas distribution channel provided in the cylindrical electrode was only on the lower side.

The gas discharge holes provided in the inner wall of the cylindrical electrode had a diameter of φ0.5 mm, and 20 gas discharge holes were arranged in the longitudinal direction.

In this example, the tubular cavity as the source gas introduction passage and the tubular cavity as the fluid introduction passage in the cylindrical electrode are configured as shown in FIGS. The number of hollow portions was changed from 2 to 120. The inner diameter of the cavity was 5 mm, and the raw material gas was introduced into the center of the cavity through a circumferential gas distribution pipe provided outside the cylindrical electrode.

The gas discharge holes provided on the inner wall of the cylindrical electrode had a hole diameter of φ0.5 mm, and 20 gas discharge holes were arranged in the longitudinal direction.

[0095] In this example, water was flowed through the tubular cavity, which was the fluid introduction flow path in the cylindrical electrode, to cool the cylindrical electrode.

[Comparative Example 1] A comparative example was produced under the same conditions as in Example 1 except that the cylindrical electrode had a double structure as shown in FIGS.

No cooling of the cylindrical electrode A cooling coil was wound along the outer wall of the cylindrical electrode,
Cool with water

[0098]

[Table 1]

The electrophotographic photosensitive members produced in Example 1 and Comparative Example 1 were evaluated by the following evaluation methods. Table 2 shows the results.

"Thickness in the axial direction of film thickness" The thickness of the deposited film was measured along the axial direction of the electrophotographic photosensitive member. % Within 10%, Δ within 10%, × over 10%
And a four-step evaluation was performed.

"Charge potential axial irregularity" The electrophotographic photosensitive member produced in an electrophotographic apparatus (a Canon NP6150 was modified for testing) was set, and the charge potential was measured in the axial direction of the electrophotographic photosensitive member. A four-step evaluation was performed, in which the case where the variation of the charged potential from the average potential was within 5% was ◎, the case where it was within 8% was ○, the case where it was within 10% was Δ, and the case where it exceeded 10% was x.

[Thickness circumferential unevenness] The thickness of the deposited film was measured along the circumferential direction for electrophotography. ○,
A four-point evaluation was performed, with Δ being within 10% and X being exceeding 10%.

[Charge Potential Circumferential Irregularity] An electrophotographic photosensitive member prepared in an electrophotographic apparatus (a Canon NP6150 was modified for testing) was set, and the charge potential was measured in the circumferential direction of the electrophotographic photosensitive member. A four-point evaluation was performed, in which ◎ indicates that the variation of the charged potential from the average potential was within 5%, ○ indicates that the variation was within 8%, and Δ indicates that the variation exceeded 10%.

"Charging Ability" Electrophotographic Apparatus (NP6 manufactured by Canon)
The electrophotographic photosensitive member prepared in (Modify 150 for testing) is set, and the charging potential at the central position in the longitudinal direction of the electrophotographic photosensitive member is evaluated as a charging ability by a relative value. However, the charging ability of the electrophotographic photosensitive member obtained in Comparative Example 1 was set to 100%.

◎: 110% <X ≦ 120% ○: 100% <X ≦ 110% Δ: X = 100% (equivalent to Comparative Example 1) X: X <100% “Image defect” Electrophotography Set the electrophotographic photoreceptor produced in the device (Canon NP6150 modified for testing),
A halftone chart (EY9-9042) manufactured by Canon Inc. was placed on a document table and black spots having a diameter of 0.2 mm or less in the same image obtained by copying were evaluated.

◎: “especially good”, ie, almost no black spots ○: “good” Δ: “no practical problem” X: “practical problem”

[0107]

[Table 2]

As is evident from Table 2, the number of tubular cavities that can be used as the source gas introduction pipe and the number of tubular cavities that can be used as the fluid introduction pipe in the cylindrical electrode are 4 or more and 100 or less.
More preferably, 10 or more and 60 or less,
Good results were obtained with unevenness in the circumferential and axial directions. In particular, good results were obtained with unevenness in the circumferential direction. Good results were also obtained with respect to image defects and charging ability in the above ranges.

[Example 2] Length 358 mm, outer diameter φ108
Using an Al holder (length: 500 mm) on which an Al cylinder (cylindrical support) having a mirror-finished surface of 1.0 mm is mounted, the Al support is mounted on the support using the apparatus shown in FIG. 1 and the apparatus shown in FIG. A light receiving layer comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was formed under the manufacturing conditions shown in Table 1.

In this example, a tubular cavity, which is a source gas introduction passage, and a tubular cavity, which is a fluid introduction passage, in a cylindrical electrode are formed by a dual method using the configuration shown in FIGS. 3, 4, and 5. The number was 40 pieces, and the inner diameter was changed between 2 mm and 25 mm. The circumferential gas distribution channel provided in the cylindrical electrode was only on the lower side.

The gas discharge holes provided on the inner wall of the cylindrical electrode had a hole diameter of φ0.5 mm, and 20 gas discharge holes were arranged in the longitudinal direction.

In this example, a tubular cavity as a raw material gas introduction passage and a tubular cavity as a fluid introduction passage in a cylindrical electrode are both formed in a structure as shown in FIGS. 3, 4 and 5. And the inner diameter was changed between 2 mm and 25 mm. The raw material gas was introduced into the center of the cavity via a circumferential gas distribution pipe provided outside the cylindrical electrode.

The gas discharge holes provided on the inner wall of the cylindrical electrode had a hole diameter of φ0.5 mm, and 20 gas discharge holes were arranged in the longitudinal direction.

In this example, the cylindrical electrode was cooled by flowing water into the tubular cavity, which is the fluid introduction channel in the cylindrical electrode.

The electrophotographic photosensitive member produced in Example 2 was evaluated in the same manner as in Experimental Example 1. Table 3 shows the results together with Comparative Example 1.

[0116]

[Table 3]

As is clear from Table 3, the inner diameter of the tubular cavity serving as the raw material gas introduction passage and the inside of the tubular cavity serving as the fluid introduction passage in the cylindrical electrode are 3 mm or more and 20 mm or less.
More preferably, when the thickness is 5 mm or more and 15 mm or less, favorable results are obtained in unevenness in the circumferential and axial directions. In particular, good results were obtained with unevenness in the circumferential direction. Regarding image defects and charging ability, good results were obtained in each case.

[Embodiment 3] Length 358 mm, outer diameter φ108
Using an Al holder (length: 500 mm) on which an Al cylinder (cylindrical support) having a mirror-finished surface of 1.0 mm is mounted, the Al support is mounted on the support using the apparatus shown in FIG. 1 and the apparatus shown in FIG. A light receiving layer comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was formed under the manufacturing conditions shown in Table 1.

In this example, a tubular cavity as a raw material gas introduction passage and a tubular cavity as a fluid introduction passage in the cylindrical electrode are formed as shown in FIG. 3, FIG. 4 and FIG. Are provided, and the circumferential gas distribution channel provided in the cylindrical electrode is provided only on the lower side.

The gas discharge holes provided on the inner wall of the cylindrical electrode had a hole diameter of φ0.5 mm, and 20 gas discharge holes were arranged in the longitudinal direction.

In this example, a tubular cavity serving as a source gas introduction passage and a tubular cavity serving as a fluid introduction passage in a cylindrical electrode are configured as shown in FIGS. 3, 4, and 5 to have an inner diameter of 10 mm. Were provided, and the raw material gas was introduced into the center of the cavity through a circumferential gas distribution pipe provided outside the cylindrical electrode.

The gas discharge holes provided on the inner wall of the cylindrical electrode had a diameter of φ0.5 mm, and 20 gas discharge holes were arranged in the longitudinal direction.

In this example, the cylindrical electrode was cooled by flowing water through the tubular cavity, which is the fluid introduction flow path in the cylindrical electrode.

The electrophotographic photosensitive member produced in Example 3 was evaluated in the same manner as in Experimental Example 1. Table 4 shows the results together with Comparative Example 1.

[0125]

[Table 4]

As is evident from Table 4, the raw material gas introduction flow path in the cylindrical electrode is formed in a tubular hollow portion so that the circumferential direction can be improved.
Good results were obtained for both the axial unevenness. In particular, good results were obtained with unevenness in the circumferential direction. In each case, good results were obtained with respect to image defects and charging ability.

[Embodiment 4] Length 358 mm, outer diameter φ108
Using an Al holder (length: 500 mm) on which an Al cylinder (cylindrical support) having a mirror-finished surface of 1.0 mm is mounted, the Al support is mounted on the support using the apparatus shown in FIG. 1 and the apparatus shown in FIG. A light receiving layer comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was formed under the manufacturing conditions shown in Table 1.

In this example, a tubular cavity as a raw material gas introduction passage and a tubular cavity as a fluid introduction passage in the cylindrical electrode are formed as shown in FIGS. Are provided, and a circumferential gas distribution channel provided in the cylindrical electrode is provided with a longitudinal distribution channel for gas supply.

The gas discharge holes provided on the inner wall of the cylindrical electrode had a hole diameter of φ0.5 mm, and 20 gas discharge holes were arranged in the longitudinal direction.

In this example, the tubular cavity as the raw material gas introduction passage and the tubular cavity as the fluid introduction passage in the cylindrical electrode are formed as shown in FIGS. Were provided in the cavity through a circumferential gas distribution pipe and a longitudinal distribution pipe provided outside the raw material cylindrical electrode. In addition, gas introduction from the gas distribution pipe in the longitudinal direction to the hollow portion was performed at a vertically symmetric distance with respect to the middle line of the entire length of the cylindrical electrode.

The gas discharge holes provided on the inner wall of the cylindrical electrode had a hole diameter of φ0.5 mm, and 20 gas discharge holes were arranged in the longitudinal direction.

In this example, the cylindrical electrode was cooled by flowing water through the tubular cavity, which is the fluid introduction flow path in the cylindrical electrode.

The electrophotographic photosensitive member produced in Example 4 was evaluated in the same manner as in Experimental Example 1. Table 5 shows the results together with Comparative Example 1.

[0134]

[Table 5]

As is clear from Table 5, the cylindrical cavity as the raw material gas introduction passage and the tubular cavity as the fluid introduction passage in the cylindrical electrode are provided, and the introduction of the raw material gas is performed in the longitudinal direction. By doing it through the distribution pipe,
Good results were obtained for both the axial unevenness. In particular, good results were obtained with unevenness in the axial direction. In each case, good results were obtained with respect to image defects and charging ability.

[Embodiment 5] 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
Using the apparatus shown in FIG. 2, a light-receiving layer comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was formed on the support under the conditions shown in Table 1.

In this example, the tubular cavity as the source gas introduction passage and the tubular cavity as the fluid introduction passage in the cylindrical electrode are configured as shown in FIGS. 3 and 4 and have an inner diameter of 10 mm. 8 (a), 20 of which are used for the charge injection blocking layer and the photoconductive layer, and the remaining 20 are used for the surface layer.
8 and the piping system shown in FIG. 8B were alternately arranged and switched during the formation of the deposited film.

The raw material gas was introduced into the center of the cavity through a circumferential gas distribution pipe provided outside the cylindrical electrode. The gas discharge hole provided in the inner wall of the cylindrical electrode has a diameter of 0.5 m.
The hole diameter was m, and 20 holes were arranged in the longitudinal direction.

[0139] In this example, water was flowed through the tubular cavity, which was the fluid introduction flow path in the cylindrical electrode, to cool the cylindrical electrode.

[Comparative Example 2] A comparative example was produced under the same conditions as in Example 5, except that the cylindrical electrode had a double structure as shown in FIGS.

The electrophotographic photosensitive members produced in Example 5 and Comparative Example 2 were evaluated by the same evaluation method as in Experimental Example 1, and the film thickness of the surface layer was evaluated by the following evaluation method.
Table 6 shows the results.

"Surface Layer Thickness Unevenness" SPECTRO MULTI CHANNEL PHO manufactured by Otsuka Electronics Co., Ltd.
Using TO DETECTOR (MODEL MC-2100), the film thickness of the deposited film was measured along the axial direction of the electrophotographic photoreceptor. Four-stage evaluation was performed in which 8% or less was evaluated as ○, 10% or less as Δ, and more than 10% as X.

"Surface layer thickness circumferential unevenness" SPECTRO MULTI CHANNEL P manufactured by Otsuka Electronics Co., Ltd.
HOTO DETECTOR (MODEL MC-2100)
The film thickness of the deposited film was measured along the circumferential direction of the electrophotographic photoreceptor, 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 10% or less was rated as Δ, and more than 10% was rated as x.

[0144]

[Table 6]

As is clear from Table 6, good results were obtained both in the circumferential direction and in the axial direction by switching and using the tubular cavity, which is the raw material gas introduction flow path in the cylindrical electrode. .

[Embodiment 6] 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
Using the apparatus shown in FIG. 2, a charge injection blocking layer, a photoconductive layer, and a photoreceptive layer comprising a surface layer were formed on the support under the production conditions shown in Table 7.

In this example, the tubular cavity as the raw material gas introduction passage and the tubular cavity as the fluid introduction passage in the cylindrical electrode are configured as shown in FIG. 3 and FIG. Are provided in each case, and 20 of them are the light of the charge injection blocking layer,
FIG. 8 (a) shows the remaining 20 layers for the surface layer for the conductive layer.
8 and the piping system shown in FIG. 8B were alternately arranged and switched during the formation of the deposited film.

In this example, 50 mL of H ₂ gas was flowed as a diluent gas into the unused cavity.

The raw material gas was introduced into the center of the cavity via a circumferential gas distribution pipe provided outside the cylindrical electrode. The gas discharge hole provided on the inner wall of the cylindrical electrode has a diameter of 0.5 mm.
And 20 were arranged in the longitudinal direction.

In this example, water was flowed through the tubular cavity, which was the fluid introduction flow path in the cylindrical electrode, to cool the cylindrical electrode.

[0151]

[Table 7]

The electrophotographic photosensitive member produced in Example 6 was evaluated by the same evaluation method as in Experimental Example 5, and good results were obtained as in Example 5.

Example 7 Example 3 was the same as Example 3 except that the number of tubular cavities serving as fluid introduction channels in the cylindrical electrode was reduced to half the number of tubular cavities serving as gas introduction channels. A charge injection blocking layer, a photoconductive layer and a photoreceptive layer comprising a surface layer were formed on the support in the same manner as in Example 3.
Good results were obtained.

[Example 8] A light emitting device comprising a charge injection blocking layer, a photoconductive layer and a surface layer was formed on the support in the same manner as in Example 3 except that the film forming conditions were prepared as shown in Table 8. When a receiving layer was prepared, good results were obtained as in Example 3.

[0155]

[Table 8]

[Example 9] [0156] Except that the film forming conditions were prepared as shown in Table 9, a light injection prevention layer, a photoconductive layer and a surface layer were formed on the support in the same manner as in Example 6. When a receiving layer was prepared, good results were obtained as in Example 6.

[0157]

[Table 9]

Example 10 A charge injection blocking layer, a charge transport layer, a charge generation layer and a surface were formed on the support in the same manner as in Example 3 except that the film forming conditions were prepared as shown in Table 10. When a light receiving layer composed of layers was produced, as in Example 3,
Good results were obtained.

[0159]

[Table 10]

Example 11 A charge injection blocking layer, a charge transport layer, a charge generation layer and a surface were formed on the support in the same manner as in Example 6, except that the film formation conditions were prepared as shown in Table 11. When a light receiving layer composed of layers was prepared, the same as in Example 6,
Good results were obtained.

[0161]

[Table 11]

[Example 12] Table 12 was obtained by the VHF-PCVD method.
A charge injection blocking layer, a charge transport layer, a charge generation layer, and a light receiving layer comprising a surface layer were formed on the support in the same manner as in Example 3 except that the film formation conditions shown in Example 3 were used. As in Example 3, good results were obtained.

Example 13 Table 13 was obtained by the VHF-PCVD method.
A charge injection blocking layer, a charge transport layer, a charge generation layer, and a light receiving layer comprising a surface layer were formed on the support in the same manner as in Example 3 except that the film formation conditions shown in Example 3 were used. As in Example 6, good results were obtained.

[0164]

[Table 12]

[0165]

[Table 13]

[0166]

According to the present invention, the inside of the cylindrical electrode constituting the vacuum chamber has a tubular cavity as a plurality of source gas introduction passages along the longitudinal direction of the cylindrical electrode, and the longitudinal direction of the cylindrical electrode. It is composed of a tubular cavity that is a fluid introduction flow path for cooling a plurality of cylindrical electrodes along the line, and the raw material gas is provided in the cylindrical electrode through the tubular cavity that is the introduction flow path. By discharging a fluid for discharging a source gas from a plurality of holes and cooling a cylindrical electrode through a tubular cavity serving as a fluid introduction flow path to form a deposited film on a cylindrical support, a deposited film is formed. The film thickness and film quality can be made uniform and the image quality can be improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically showing an arrangement of a cylindrical electrode and a counter electrode including a cylindrical support in a deposition film forming apparatus using a plasma CVD method of the present invention.

FIG. 2 is a schematic sectional view of a deposited film forming apparatus according to another embodiment of the present invention.

FIG. 3 is a schematic top sectional view showing a hollow portion provided in a cylindrical electrode.

FIG. 4 is a schematic sectional view showing a cavity provided in a cylindrical electrode.

FIG. 5 is an explanatory diagram showing a piping system.

FIG. 6 shows a conventional high-frequency plasma CVD method (hereinafter “PCV”).
D) (abbreviated as "D").

FIG. 7 is a schematic configuration diagram showing a cylindrical electrode constituting a vacuum chamber in a conventional device.

FIG. 8 is an explanatory view showing a piping system in a case where a hollow portion provided in a cylindrical electrode is switched and used in a deposition film forming apparatus using a plasma CVD method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 101 Cylindrical electrode 102 Counter electrode including a cylindrical support 103 Cavity part which is a source gas introduction means (flow path) 104 Cylindrical electrode inner wall 105 Heater for heating a support 106 High frequency power introduction part 107 Upper insulator 108 Lower insulator 109 Gas discharge hole 110 Inner circumferential gas distribution pipe at lower part of cylindrical electrode 111 Inner circumferential gas distribution pipe at upper part of cylindrical electrode 112 Raw material gas inlet 113 Exhaust line 114 Longitudinal gas distribution pipe 115 Circumferential gas distribution pipe 116 Fluid introduction means Cavity part (flow path) 117 Fluid inlet port 118 Cylindrical electrode lower circumferential fluid distribution pipe 119 Cylindrical electrode upper circumferential fluid distribution pipe 120 Fluid outlet 201 Cylindrical electrode 202 Counter electrode including cylindrical support 203 Source gas inlet 204 Inner wall of cylindrical electrode 205 Heater for supporting body heating 206 High frequency power Force introduction part 207 Upper insulator 208 Lower insulator 209 Gas discharge hole 210 Exhaust line 301-316 Automatic opening / closing valve 307, 308 Circumferential gas distribution pipe 309, 310 Source gas inlet 317 Fluid inlet 318 Inner circumference of lower part of cylindrical electrode Directional fluid distribution pipe

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hideaki Matsuoka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kazuhiko Takada 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Koji Hitsuishi 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) in Canon Inc. 2H068 DA00 EA24 4K030 AA06 AA17 AA24 BA30 CA02 CA16 EA05 EA06 FA03 KA15 KA26 KA30 LA17 5F045 AA08 AB04 AC01 AC02 AD06 AF10 BB02 BB08 CA16 DA52 DP25 EC07 EE20 EF03 EH04 EJ05 EJ09

Claims (9)

[Claims] 1. A cylindrical electrode forming at least a part of a side wall of a reaction chamber, a vacuum-tight airtight reaction space provided in an inner peripheral surface of the cylindrical electrode, and a deposited film in the reaction space. A substrate holder for installing a cylindrical substrate for forming; a source gas introducing means for introducing a source gas into the reaction space; and a glow discharge by exciting the source gas introduced into the reaction space. An apparatus for producing a deposited film by a plasma CVD method, comprising: a high-frequency energy introducing unit that introduces high-frequency energy for generating using the cylindrical electrode; and an exhaust unit that exhausts the reaction space. The side wall has a plurality of cooling tubular cavities through which a cooling fluid of the cylindrical electrode flows, and a plurality of source gas tubular cavities for supplying a source gas to the source gas introducing means. Part each manufacturing apparatus of the deposited film, which are arranged extending along the axial direction from the bottom portion of the cylindrical electrodes to the head of the. 2. The apparatus for producing a deposited film according to claim 1, wherein the raw material gas tubular cavity is connected to at least one of a circumferential gas distribution channel and a longitudinal gas distribution channel. 3. The tubular cavity for a source gas has a mechanism capable of supplying a source gas according to a gas type or a layer configuration for forming a deposited film, and switches a tubular cavity to be operated as necessary. The apparatus for producing a deposited film according to claim 1, wherein the apparatus can be used by using. 4. The production of a deposited film according to claim 1, wherein said cooling tubular cavity is connected to a circumferential fluid distribution channel at the head and bottom of said reaction chamber. apparatus. 5. A cylindrical substrate is placed in a reaction space formed in an inner peripheral surface of a cylindrical electrode constituting at least a part of a side wall of a reaction chamber, and the reaction space is vacuum-tightly sealed to introduce a raw material gas. A method for producing a deposited film by a plasma CVD method, comprising applying a high-frequency energy to excite the source gas to generate a glow discharge and forming a deposited film on the cylindrical substrate. A plurality of cooling tubular cavities through which the cooling fluid of the cylindrical electrode flows, and a plurality of raw material gas tubular cavities for supplying a raw material gas to the raw material gas introducing means are provided. A method for producing a deposited film, comprising cooling a cylindrical electrode and supplying a source gas to said source gas introducing means. 6. The production of a deposited film according to claim 5, wherein the gas is supplied to the raw material gas tubular cavity through a gas distribution channel extending in at least one of a circumferential direction and a longitudinal direction. Method. 7. The source gas is supplied to the source gas tubular cavity by a mechanism provided to supply the source gas for each gas type for forming a deposited film or for each layer configuration, if necessary. 7. The method for producing a deposited film according to claim 5, wherein the activated tubular cavity is switched and used. 8. The supply and discharge of fluid to and from the source gas tubular cavity is performed by circumferential fluid distribution provided at the head and bottom of the reaction chamber connected to the source gas tubular cavity. The method for producing a deposited film according to claim 5, wherein the method is performed through a flow path. 9. The deposition film according to claim 5, wherein the supply of the fluid to the cooling fluid flow passage forming a part of the raw material gas tubular cavity is performed from a lower side of the cylindrical electrode. Production method.