JPH10176271A - Deposited film forming apparatus and deposited film forming method - Google Patents

Abstract

(57) [Problem] To easily form a deposited film having excellent uniformity of characteristics while suppressing rotational blurring of a substrate. SOLUTION: A rotary driving means (rotating shaft 109, gear 110, rotary motor 111, etc.) for holding and rotating one end of the cylindrical conductive substrate 101 is provided, and is surrounded by a plurality of cylindrical conductive substrates 101. An inner chamber 112, which is an open space, is formed, and further supports one end of a cylindrical conductive substrate 101 in a deposition film forming apparatus provided with a gas discharge tube 108 for introducing a raw material gas and an electrode 105 for applying high frequency power. And a rotation assisting means (bearing or the like) 103 for assisting rotation of the deposited film; and a method of forming a deposited film using the device.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a functional deposition film (for example, a semiconductor device, a light receiving member for electrophotography, a line sensor for image input, an imaging device, a photovoltaic device, etc.) on a cylindrical conductive substrate. Film forming apparatus (plasma CV) for forming an amorphous semiconductor film used for
D apparatus) and a method for forming a deposited film using this apparatus.

[0002]

2. Description of the Related Art Amorphous silicon, hydrogen and / or halogen are used as element members for semiconductor devices, light receiving members for electrophotography, line sensors for image input, imaging devices, photovoltaic devices, and various other electronic elements. Deposited films such as semiconductor films composed of compensated amorphous materials such as amorphous silicon have been proposed, and some of them have been put to practical use. However, some of these devices have problems in terms of manufacturing cost and the like. For example, when a light-receiving member for electrophotography is manufactured, a relatively thick film thickness is required, so that the deposition time of the film is inevitably long, and the manufacturing cost is high. Against this background, there has been a demand for a deposited film forming apparatus capable of improving productivity and improving efficiency at various points.

[0003] As a deposited film forming apparatus which solves such a problem, Japanese Patent Application Laid-Open No. 60-186849 discloses a method of forming a deposited film by a plasma CVD method using microwaves. Specifically, an internal chamber is formed by arranging a plurality of cylindrical members in a deposition chamber, thereby increasing gas utilization efficiency and improving productivity, and decomposing a raw material gas and a raw material gas therein. A method of forming a deposited film over the entire circumference of a substrate by introducing microwave power and rotating a cylindrical substrate is disclosed. Japanese Patent Application Laid-Open No. Hei 3-219081 discloses a method for forming a deposited film of higher quality by applying a DC electric field to a plasma space and controlling the plasma potential. Japanese Patent Application Laid-Open No. 6-242624 discloses that
There is disclosed a method in which a raw material gas is decomposed by using an electromagnetic wave of 450 MHz to modify an interface portion of each layer to provide an excellent electrophotographic photosensitive member.

Here, an example of a conventional deposited film forming apparatus will be described with reference to the drawings. FIG. 4A is a schematic diagram of a longitudinal section showing an example of a conventional device, and FIG. 4B is a schematic diagram of a cross section thereof. The apparatus shown in FIG.
0, the electrode 405 and the gas discharge pipe 408 for the raw material gas.
And a plate 402, and a cylindrical conductive substrate 401 is disposed around the electrode 405. The cylindrical conductive substrate 401 is rotated by a rotating mechanism (a rotating shaft 409, a gear 410,
It is rotated by a rotation motor 411). Power supply 40
6 is connected to an electrode 405 through a matching box 407 so that high-frequency power can be applied.
The source gas introduced into the internal chamber 412 is decomposed by the discharge energy, and a predetermined deposition film is formed over the entire circumference of the substrate 401 by rotating the base 401. Further, the exhaust gas is exhausted from the exhaust port 404.

[0005]

In the conventional deposited film forming apparatus shown in FIG. 4, when the length in the axial direction becomes longer than the outer diameter of the cylindrical conductive substrate 401, the perpendicularity of the shaft is reduced. Accuracy becomes severe, axis deviation tends to occur when the substrate 401 rotates, and a problem may occur in the uniformity of the deposited film. Furthermore, the problem of plasma instability due to axis deviation also occurs at the same time, which is one of the causes that the characteristics of the deposited film vary and the reproducibility is adversely affected. Such a variation in characteristics affects the yield, and even if the production efficiency is improved, it has been a factor that increases the cost of the device to be manufactured as a result.

[0006] In addition, shaft distortion due to physical strain applied to the chamber in a vacuum state, distortion of each part due to heating and cooling cycles, and the like have also become serious problems. As a result, there has been a problem that the plasma state becomes non-uniform in the axial direction, and furthermore, the discharge becomes unstable. Due to such a change in the plasma state, unevenness in characteristics of the deposited film, a decrease in characteristics affected by plasma, a decrease in reproducibility, and the like are likely to occur. Further, the above-described chamber distortion is related to the processing accuracy, material, wall thickness, etc. of the chamber body, but there are problems in terms of cost, production, and processing accuracy in order to completely suppress the distortion. .

In recent years, in particular, in recent years, there has been an increase in the demand for photoconductors as printers as well as for downsizing of copiers and for amorphous silicon photoconductors having a smaller diameter than before. The effects of blurring are becoming a more serious problem.

Further, in recent years, the performance of copying machines has been improved, and with the spread of digital machines and color machines, photoconductors have become
Higher image quality and higher quality than ever have been demanded, and even more uniform deposition films have been demanded.

An object of the present invention is to solve the problems of the prior art as described above. That is, an object of the present invention is to provide a deposited film forming apparatus which can easily form a deposited film which is excellent in gas use efficiency and production stability, and which is excellent in uniformity of film thickness and characteristics, and a deposited film forming method using the same. Is to provide.

[0010]

According to the present invention, there is provided a rotary driving means for holding one end of a cylindrical conductive base and rotating the cylindrical conductive base about a cylindrical axis, wherein the rotary driving means is provided with the cylindrical conductive base. A plurality of substrates are arranged on the same circumference in the reaction vessel so as to form an internal chamber which is a space surrounded by the cylindrical conductive substrate. Means for introducing a gas, and means for applying a high-frequency power for decomposing the source gas, in a deposited film forming apparatus, wherein a side of the cylindrical conductive substrate that is not held by the rotation driving means What is claimed is: 1. A deposition film forming apparatus comprising: a rotation assisting unit for supporting one end and assisting rotation. The deposition film forming apparatus of the present invention is used to deposit a deposition film on a cylindrical conductive substrate. Specially to form A deposited film forming method according to.

In the present invention, one end of the cylindrical conductive base which has not been conventionally supported is supported by the rotation assisting means, that is, the rotation axis of the cylindrical conductive base is supported from both ends, and one end is held. By using a mechanism that assists rotation by driving while rotating and supporting the other end only, it is possible to satisfactorily suppress rotational deflection of the cylindrical conductive substrate due to shaft accuracy and device distortion, etc. The state and the stability of discharge are also improved, and the above object can be achieved.

[0012]

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

FIG. 1A is a schematic diagram of a longitudinal section showing an example of the deposited film forming apparatus of the present invention, and FIG. 1B is a schematic diagram of a cross section thereof. The apparatus shown in FIG. 1 is provided with a rotation driving means for holding the lower end of the cylindrical conductive base 101 and rotating the cylindrical conductive base 101 about a cylindrical axis. This rotation driving means is constituted by a mechanism for rotating a rotation shaft 109 connected to the cylindrical conductive base 101 via a gear 110 by a rotation motor 111. Then, the cylindrical conductive substrate 101
Is located on the same circumference around the electrode 105 in the reaction vessel 100 that can be decompressed, thereby forming a cylindrical space (internal chamber 112) surrounded by the cylindrical conductive substrate 101.
Is formed. An electrode 105 for applying a high-frequency power for decomposing a source gas in the inner chamber 112 is provided at the center of the inner chamber 112 and connected to a high-frequency power source 106 via a matching box 107. Further, gas discharge tubes 108 for introducing a source gas into the inner chamber 112 are provided on all sides with the electrode 105 as a center. An exhaust port 104 is provided above the reaction container 100. The plate 102 is provided on the upper surface of the inner chamber 112.
In this apparatus, by forming the internal chamber 112 surrounded by the plurality of cylindrical conductive substrates 101 and the plate 102, the utilization efficiency of gas and the like and the productivity are further improved.

Further, the apparatus has a cylindrical conductive substrate 10.
The plate 102 is provided with rotation assisting means 103 for supporting the upper end of the first member 1 and assisting the rotation. By the rotation assisting means 103, the rotational deviation of the cylindrical conductive substrate 101 can be suppressed, and a deposited film having excellent uniformity of film thickness and characteristics over the entire circumference of the substrate can be obtained with high productivity.

Next, a method for forming a deposited film on the cylindrical conductive substrate 101 using the deposited film forming apparatus shown in FIG. First, a plurality of substrates 101, which have been degreased and washed in advance, are placed on the same circumference around the electrode 105 in the reaction vessel 100. Thus, an internal chamber 112 is formed as shown in FIG. Next, the inside of the reaction vessel 100 is evacuated by an exhaust device (not shown) (for example, a vacuum pump). Next, the temperature of the base 101 is controlled to a desired temperature by a heater (not shown). When the temperature of the substrate 101 reaches a desired temperature, a source gas is supplied from a source gas supply system (not shown) into the internal chamber 112 through a gas discharge pipe 108. At this time, care should be taken not to cause extreme pressure fluctuation such as gas projection. Next, when the flow rate of the raw material gas reaches a desired flow rate, a vacuum gauge (not shown)
And adjusting the exhaust valve (not shown) to obtain a desired internal pressure.

When the internal pressure is stabilized, the rotation driving means 1
The base 101 is rotated by 09 to 111 to set the high-frequency power supply 106 to a desired power. This high-frequency power is applied to the electrode 105 through the matching box 107. The source gas introduced into the inner chamber 112 is decomposed by the discharge energy by the high frequency power. Here, by rotating the base 101, a desired deposited film is formed over the entire circumference. After the formation of a deposited film having a desired film thickness, the supply of high-frequency power is stopped, and the flow of gas into the reaction vessel 100 is stopped. Note that when a deposited film including a plurality of layers is formed on the substrate 101 in order to obtain desired characteristics of the deposited film, the above operation may be repeated.

In the present invention, the rotation assisting means 103 includes:
Preferably, it is installed on the plate 102 forming the internal chamber 112. As the rotation assisting means 103, the inner diameter of the cylindrical conductive base 101 is loose so that one end of the cylindrical conductive base 101 (the end on the side not held by the rotation driving means) can be supported. It is preferable that the means has a function of positioning and rotating a bearing or the like having substantially the same outer circumference as far as possible. That is, in the present invention, the rotation assisting means is a means for preventing deviation of rotation or the like and assisting to perform good rotation. When a bearing is used as the rotation assisting unit 103, a non-oil type bearing is preferable in consideration of driving in a vacuum and mixing of impurities into a deposited film. The material is preferably ceramic, metal-based solid lubricating composite material (Coruze Metal: Fuji Dice Co., Ltd.) or the like.

However, in the present invention, the rotation assisting means 10
3 is not limited to bearings. Other than bearings, for example, belts, rotating gears, etc. can be used.

In the present invention, it is preferable that the plate 102 forms the internal chamber 112 and can be provided with the rotation assisting means 103. The shape and size of the plate 102 are not particularly limited as long as both functions can be achieved. There is also no particular limitation on the material, and any material can be used as long as it can withstand the use environment, such as strength, temperature, and plasma. For example, Al, Ti,
Metals such as Cr, Fe, Ni and Co, alloys of these metals such as stainless steel, and ceramics represented by Al ₂ O ₃ are generally used. It is also effective to roughen these surfaces to improve the adhesion of the deposited film, to perform ceramic spraying, or the like. For example, at least the surface of the plate on the inner chamber side is made of Al ₂ O ₃ or Al,
It is effective to roughen the surface by thermal spraying with a metal material such as Ti, Cr, Ni or other methods.

In the present invention, the frequency of the high-frequency power introduced into the reaction vessel 100 is not particularly limited. However, according to the experiments of the present inventors, in order to improve production efficiency,
When the number of tubes per lot is increased and the volume of the inner chamber 112 is increased to determine the spread of discharge, the frequency is 2
If the frequency is less than 0 MHz, it may be difficult to maintain the discharge depending on the conditions. Further, when the pressure in the reaction vessel is increased to maintain the discharge, non-products of silicon called polysilane are generated in the reaction vessel 100 at the same time as the bias of the discharge, which may lower the productivity. . On the other hand, if the frequency is higher than 450 MHz, the transmission characteristics of the high-frequency power deteriorate, and when the high-frequency power is considerably smaller than the power for completely decomposing the source gas (source gas decomposition saturation power), the plasma becomes unstable. There is. According to the findings of the present inventors including these points, the frequency of the high-frequency power is set to 20 MHz because the target deposited film can be formed more favorably even in a mass production apparatus such as the configuration of the present invention.
It is desirable to use an electromagnetic wave in the range of 450 MHz to 450 MHz, and more preferably in the range of 50 MHz to 450 MHz.

In the present invention, a high frequency is applied to the reaction vessel 100.
The electrode 108 serving as a means for introducing into the inside is positioned at the center of the inner chamber 112 (that is, the center of the circumference when the plurality of cylindrical conductive substrates 101 are arranged on the same circumference). Is preferred. The material of the electrode 108 may be basically any conductive material, for example, stainless steel, Al, Cr, Mo, Au,
In, Nb, Ni, Te, V, Ti, Pt, Pb, Fe
Metals such as these, alloys thereof, or those provided with ceramic spraying or a cover on the surface thereof for improving the adhesion of the deposited film are usually used.

As a source gas for the deposited film, for example, a source gas for forming an amorphous silicon such as silane (SiH ₄ ) or disilane (Si ₂ H ₆ ), or a source gas for forming a functional deposited film such as germane (GeH ₄ ) or the like. Mixed gas. Hydrogen (H ₂ ), helium (H
e), argon (Ar) and the like.

As a characteristic improving gas for changing the band gap width of the deposited film, an element containing a nitrogen atom such as nitrogen (N ₂ ) and ammonia (NH ₃ ); oxygen (O ₂ ), nitrogen oxide (NO) ), Dinitrogen oxide (N ₂ O) and other oxygen-containing elements; methane (CH ₄ ), ethane (C ₂ H ₆ ), ethylene (C ₂ H ₄ ), acetylene (C ₂ H ₂ ), propane (C
₃ H ₈₎ or the like of a hydrocarbon, silicon tetrafluoride (SiF _4), disilicon hexafluoride (Si ₂ H _6), germanium tetrafluoride (Ge
Fluorides such as F ₄ ); and a mixed gas thereof. For the purpose of doping, diborane (B
₂ H ₆ ), boron fluoride (BF ₃ ), phosphine (PH ₃ )
It is also effective to introduce dopant gas such as at the same time.

The substrate 101 used in the present invention may be any substrate as long as it is cylindrical and conductive. Examples of the material include Al, Cr, Mo, Au, In, and N.
Metals such as b, Te, V, Ti, Pt, Pb, and Fe, and alloys thereof (for example, stainless steel). Also,
Polyester, polystyrene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride,
It is also possible to use a sheet of a synthetic resin such as polyethylene, polyamide or the like, or an electrically insulating substrate such as glass, ceramic or the like, on which at least the surface on the side on which the deposited film is formed is subjected to a conductive treatment. In this case, it is desirable that the side opposite to the side on which the deposited film is formed is also subjected to a conductive treatment.

The surface shape of the cylindrical substrate 101 can be a smooth flat surface or an uneven surface. For example, when performing image recording using a coherent light such as a laser beam with a light receiving member for electrophotography or the like, Japanese Patent Application Laid-Open No. 60-168 discloses a method for eliminating image defects due to interference fringe patterns appearing in visible images.
Nos. 156, 60-178457 and 60-178.
An uneven surface produced by a known method described in, for example, JP-A-225854 can be used.

The temperature of the substrate 101 at the time of forming the deposited film is effective at any temperature, but is preferably 20 ° C. or more and 500 ° C. or less, particularly 50
It is preferable that the temperature is not lower than 450 ° C.

FIG. 2 shows that a-Si can be produced according to the present invention.
FIG. 3 is a schematic cross-sectional view illustrating a layer configuration of a photoconductor. The photoreceptor shown in this figure is a blocking type photoreceptor in which a charge injection blocking layer 202, a photoconductive layer 203, and a surface protection layer 204 are formed on a conductive substrate 201 in this order by a layer design. In order to manufacture such a photoreceptor and to form a deposited film by the glow discharge method using the apparatus of the present invention, a source gas for supplying Si that can supply silicon atoms (Si) is basically used. A source gas for supplying H that can supply hydrogen atoms (H) and / or a source gas for supplying X that can supply halogen atoms (X) are introduced into the internal chamber in a desired gas state, and glowing is performed. Discharge is caused, and a-S is placed on a predetermined cylindrical substrate 101 previously set at a predetermined position.
i: A layer composed of H and X may be formed.

Examples of substances that can be used as a gas for supplying Si include:
Silicon hydrides (silanes) in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ or capable of being gasified can be used effectively. Furthermore, in terms of ease of handling at the time of layer production and good Si supply efficiency, SiH ₄ ,
Si ₂ H ₆ is mentioned as a preferable example.

Then, in order to introduce hydrogen atoms structurally into the deposited film to be formed, to further easily control the introduction ratio of hydrogen atoms, and to obtain desired film characteristics, these gases are further added with H ₂ and H _2. A layer of He or a gas of a silicon compound containing a hydrogen atom can also be mixed in a desired amount. Further, each gas may be mixed not only with a single species but also with a plurality of species at a predetermined mixture ratio.

Preferred examples of the source gas for supplying halogen atoms include gaseous or gasifiable halogen compounds such as halogen gas, halides, interhalogen compounds containing halogen, and silane derivatives substituted with halogen. No. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom and containing a silicon atom and a halogen atom as constituent elements is also an effective example. Particularly preferred halogen compounds include fluorine gas (F ₂ ), BrF, ClF, and Cl.
Inter-halogen compounds such as F ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned. As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, for example, silicon fluoride such as SiF ₄ or Si ₂ F ₆ can be mentioned as a preferable example.

To control the amount of hydrogen atoms and / or halogen atoms contained in the deposited film, for example, the temperature of the substrate,
What is necessary is just to control the amount of the raw material used to contain hydrogen atoms and / or halogen atoms into the reaction vessel, the discharge power and the like. 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 state of being uniformly distributed, or there may be a part containing the atoms in the layer thickness direction in a non-uniform distribution state. . Examples of the atoms that control the conductivity include so-called impurities in the semiconductor field, and atoms belonging to Group IIIb of the Periodic Table that provide p-type conduction characteristics (hereinafter, “Group IIIb atoms”)
Abbreviated as ") or Vb of the periodic table giving n-type conduction characteristics.
An atom belonging to the group (hereinafter abbreviated as “Group Vb atom”) can be used. As the Group IIIb atom, specifically, boron (B), aluminum (Al), gallium (G
a), 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. In particular, P and As
Is preferred.

The content of the atoms controlling the conductivity contained in each layer is appropriately determined as desired for each layer.
１1 × 10 ⁴ atomic ppm, more preferably 50-5 × 1
0 ³ atomic ppm, optimally 1 × 10 ² to 1 × 10 ³ atomic p
pm. In the photoconductive layer 203, preferably 1
× 10 ^-2 to 1 × 10 ⁴ atomic ppm, more preferably 5 ×
10 ^{−2 to} 5 × 10 ³ atomic ppm, optimally 1 × 10 ⁻¹ to
1 × 10 ³ atomic ppm.

In the surface protective layer 204, atoms for controlling conductivity may be introduced simultaneously with the formation. Preferably from 10 to 1 × 10 ⁴ atomic ppm, more preferably from 50 to
5 × 10 ³ atomic ppm, optimally 1 × 10 ² to 1 × 10
^{It is 3} atomic ppm. Atoms that control conductivity, for example
In order to structurally introduce a group IIIb atom or a group Vb atom, a source material for introducing a group IIIb atom or a source material for introducing a group Vb atom in a gaseous state in a reaction vessel during layer formation. Then, it may be introduced together with another gas for forming a deposited film. As a source material for introducing a Group IIIb atom or a source material for introducing a Group Vb 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 a raw material for introducing a Group IIIb atom, specifically, for introducing a boron atom, B 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 H
₁₄ borohydride; and boron halide such as BF ₃ , BCl ₃ , and BBr ₃ . In addition, AlCl ₃ , Ga
Cl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like can also be mentioned. The source material for introducing a group Vb atom is effectively used as a source material for introducing a phosphorus atom.
₃ , hydrogenated phosphorus such as P ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ ,
Phosphorus halides such as PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , PI _{3 and the} like. In addition, AsH ₃ , AsF ₃ , A
sCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , S
bF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ ,
BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing Group Vb atoms. In addition, these raw materials for introducing atoms for controlling conductivity may be diluted with H ₂ and / or He as necessary.

In order to form a deposited film having desired film characteristics, the mixing ratio between the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power, and the substrate temperature may be appropriately set. The flow rate of H ₂ and / or He used as a diluent gas is appropriately selected in an optimum range according to the layer design. However, the flow rate of H ₂ and / or He to the Si supply gas is usually 1 to 20 times, Preferably 4 to 15 times, optimally 5
It is desirable to control to a range of 10 to 10 times. Be appropriately selected within an optimum range in accordance with the designing of layer configuration the gas pressure in the reaction vessel is also usually 1 × 10 ^-5 to 10 Torr, preferably 5 × 10 ^-5 ~5Torr, optimally 1 × 10 ^{- Four}
１1 Torr. Similarly, the optimum range of the discharge power is 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 set to 1 to 100.
It is desirably set to a range of 2 times, preferably 2 to 80 times, and optimally 3 to 50 times. The optimum temperature of the substrate is appropriately selected according to the layer design.
Desirably, the temperature is 0 to 350 ° C.

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

The present invention further provides a photoreceptor for a copying machine or a printer, such as a high-resistance amorphous photoreceptor and a function-separated type amorphous photoreceptor, in addition to a blocking amorphous photoreceptor.
It can be applied to the fabrication of any device.

[0038]

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

<Experimental Example, Comparative Experimental Example> In the deposited film forming apparatus shown in FIG. 1, a circular through hole was made in the plate 302 as shown in FIG. A through hole was provided to support the upper end of the cylindrical conductive substrate 301 and assist rotation. Using the apparatus shown in FIG. 1 and FIG. 3, an aluminum cylinder having an outer diameter of 30 mm, a length of 360 mm, and a thickness of 2.5 mm is mirror-finished, degreased and washed, and used as a cylindrical conductive substrate. Under the conditions shown in Table 1 below, discharge stability was checked according to the method described below.

On the other hand, as a comparative experiment example, the apparatus shown in FIG. 4 having no rotation assisting means was used, and under the conditions shown in Table 1 below (however, the high frequency was only 105 MHz), as in the experiment example, The stability of the discharge was checked according to the method described.

[0041]

[Table 1] [Evaluation of Discharge Stability] The change in reflection of the discharge for 60 minutes was monitored, and the discharge stability was evaluated based on the change. Regarding discharge stability, ◎ indicates “no change and stable” ○ indicates “small change but several times stable” ▲ indicates “small change and several large changes and is slightly unstable” △ indicates “large change” Is unstable many times, and "x" indicates "discharge cannot be maintained for 60 minutes." Further, * indicates that polysilane was generated in the reaction vessel at the end of the reaction.

Tables 2 to 6 below show the results of evaluation of discharge stability and polysilane formation for each frequency (however, only comparative examples in Table 4).

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

[Table 6] As shown in Tables 2 to 6, in the experimental example, the frequency range was 20M.
Good results were obtained in the frequency range from Hz to 450 MHz, and particularly good results were obtained in the range from 50 MHz to 450 MHz. Further, as shown in Table 5, in the comparative experimental example, inferior results were obtained as compared with the experimental example under the same conditions.

<Embodiment 1 and Comparative Example 1> In the embodiment 1, the corrugated metal (manufactured by Fuji Dice Co., Ltd.) was used as the bearing material of the rotation assisting means 303 shown in FIG. In the same manner as in the experimental example, the rotation assisting means of the deposited film forming apparatus shown in FIG. 1 was configured as shown in FIG. 3 except that the surface of the SUS306 on the inner chamber side was sprayed with alumina. (Bearing) 303 is provided. Using this apparatus, an aluminum cylinder having an outer diameter of 30 mm, a length of 360 mm, and a thickness of 2.5 mm was mirror-finished, degreased and washed, and used as a cylindrical conductive substrate under the conditions shown in Table 7 below. The charge injection blocking layer 202 and the photoconductive layer 20 shown in FIG.
3. A blocking type electrophotographic light receiving member (hereinafter, referred to as a drum) having a layer structure composed of the surface layer 204 was manufactured.

On the other hand, in Comparative Example 1, an aluminum cylinder having an outer diameter of 30 mm, a length of 360 mm and a wall thickness of 2.5 mm was used in the same manner as in Example 1 except that the apparatus shown in FIG. The mirror shown in FIG. 2 was subjected to mirror finishing, degreased and washed, and used as a cylindrical conductive substrate to produce a drum shown in FIG. 2 under the conditions shown in Table 8 below.

[0050]

[Table 7] The drum thus manufactured was set in an electrophotographic apparatus (NP6030 manufactured by Canon Inc. was modified for testing), and the electrophotographic properties and image quality were evaluated according to the following methods.

[Halftone image unevenness] A halftone chart (part number FY9-9042) manufactured by Canon was placed on a document table, irradiated with normal exposure and twice as much exposure, and a copy was taken. The image density of 100 points was measured with a circular area having a diameter of 5 mm as one unit, and the variation in the density was evaluated. Regarding the halftone image unevenness, ◎ indicates “particularly good”, ○ indicates “good”, Δ indicates “no problem in practical use”, and × indicates “problem in practical use”.

[Differences in Sensitivity and Charging Temperature Characteristics within the Same Lot] Variations in potential characteristics were evaluated for two items of one sensitivity and two charging temperature characteristics of drums manufactured in the same lot.

1. Sensitivity: The drum was charged to a constant dark area surface potential and immediately irradiated with a light image. Here, a xenon lamp light source was used, a filter was used to irradiate light excluding light in a wavelength range of 600 nm or more using a filter, and the surface potential of the bright portion of the drum was measured with a surface voltmeter. The exposure amount was adjusted so that the bright portion surface potential became a predetermined potential, and the exposure amount at this time was used as the sensitivity.

2. Charging temperature characteristic: The drum is charged to a constant dark area surface potential, and the temperature of the drum is raised from room temperature to about 45 ° C.
, And the change in the charging ability per 1 ° C. temperature was measured.

For each of the above-described 1 sensitivity and 2 chargeability temperature characteristics, ◎ indicates “particularly good”, 〇 indicates “good”, Δ indicates “no problem in practical use”, and x indicates “problem in practical use”. Was passed.

The evaluation results are shown in Table 8 below.

[0057]

[Table 8] As shown in Table 8, the drum manufactured in Example 1 showed better results in all evaluation items than the drum manufactured in Comparative Example 1.

<Embodiment 2> A drum was manufactured under the same conditions as in Embodiment 1 except that a ceramic bearing (non-oil) or a stainless steel bearing (using a lubricant) was used as the material of the rotation assisting means 303. did. The produced drum was set in the same device as in Example 1, and the same evaluation as in Example 1 was performed. In addition, the following image characteristics were evaluated. Furthermore, the same evaluation was also performed on the drum manufactured in Example 1.

[Image deletion] Canon test chart consisting of whole characters on a white background (part number FY9-9058)
Was placed on a platen, irradiated at twice the normal exposure, a copy was taken, the resulting image was observed, and it was evaluated by the following four steps whether fine lines on the image were connected without interruption. When there was unevenness in the image, the evaluation was made at the worst part in the entire image area. Regarding image flow, ◎ indicates “good” ○ indicates “partially interrupted” △ indicates “there are many interruptions but can be read as characters, and there is no practical problem” × indicates “there are many discontinuities that are difficult to read as characters, and there is a practical problem” And ◎ and ○ were accepted.

[Memory potential] Process speed 380
mm / sec, pre-exposure (700nm LED) 4l
Under a condition of ux · sec, a halogen lamp was used as an image exposure light source, and the surface in an unexposed state was measured by a potential sensor of a surface electrometer (trade name: Model 344, set by TREK) set at a developing device position of an electrophotographic apparatus. The potential difference between the potential and the time when the surface was exposed and then charged again was measured. Regarding the memory potential, ◎ indicates “especially good”, は indicates “good”, Δ indicates “no problem in practical use”, and x indicates “problem in practical use”.

Table 9 shows the evaluation results of the drums manufactured under the respective conditions.

[0062]

[Table 9] As shown in Table 9, good results were obtained in all the items when ceramic or corrugated metal was used as the material of the rotation assisting means. As for the stainless steel material, although the image flow and the memory potential were slightly inferior to those of the above two types of materials, the results were at a level of no problem in practical use.

<Embodiment 3> Stainless steel, Al, Ni and Ti metals and alumina (Al)
₂ O ₃ )
A drum was manufactured under the same conditions as in Example 1, and the same evaluation was performed. Table 10 shows the results.

[0064]

[Table 10] As shown in Table 10, the drum manufactured in this example was
Good evaluation results similar to those of Example 1 were obtained for all plate materials.

<Embodiment 4> A stainless steel plate was used as the plate.
, Al, Ni, Ti metals and alumina (Al _Two O
_Three ) The surface on the inner chamber side is roughened with each material
Using the processed one, under the same conditions as in Example 1,
Then, the same evaluation was performed. Made in this example
For the drum, the same good evaluation results as in Example 1 were obtained.

Further, it was confirmed that the adhesion of the deposited film adhered to the plate was improved by roughening the plate. As a result, in the drum manufactured in this example, it was confirmed that the defects of the deposited film were reduced and the white spot level in the image of the drum was improved. In addition,
Here, “white spots” refers to a 0.2 mm diameter within the same area of an image obtained when a full-face black chart made by Canon (part number: FY9-9073) is placed on a document table and copied.
These white points are referred to.

<Embodiment 5> Stainless steel, Al, Ni, T
Example 1 Using a plate made of a material of each metal of i and spraying alumina (Al ₂ O ₃ ) on the inner chamber side surface,
A drum was produced under the same conditions as described above, and the same evaluation was performed.
In the drum manufactured in this example, the same good evaluation result as in Example 1 was obtained. Furthermore, as in Example 4, it was confirmed that the white spot level in the image of the drum was improved.

[0068]

According to the present invention, it is possible to suppress the rotational deviation due to the axial accuracy of the cylindrical conductive substrate, the distortion of the chamber, etc., and to improve the gas use efficiency, the productivity, and the uniformity of the film thickness and characteristics. An excellent deposited film can be stably formed at low cost. For example, when an electrophotographic light-receiving member or the like is manufactured according to the present invention, very excellent effects can be obtained particularly in terms of halftone unevenness in an image, sensitivity variation within the same lot, and variation in charging ability temperature characteristics. .

The present invention relates to a method for forming a functional deposition film such as an amorphous semiconductor used for a semiconductor device, a light receiving member for electrophotography, a line sensor for image input, an imaging device, a photovoltaic device, etc. by a plasma CVD method. Very useful. In particular, it is very suitable for the manufacture of small-diameter drums with the recent miniaturization of copying machines and the high image quality and high quality of the drums with the high performance of the copying machine body.

[Brief description of the drawings]

FIG. 1A is a schematic diagram of a longitudinal section showing an example of a deposited film forming apparatus of the present invention, and FIG. 1B is a schematic diagram of a cross section thereof.

FIG. 2 is a schematic cross-sectional view illustrating a layer configuration of an a-Si photosensitive member that can be manufactured according to the present invention.

FIG. 3 is a schematic diagram showing a rotation assisting unit used in an experimental example and an example.

FIG. 4A is a schematic diagram of a longitudinal section showing an example of a conventional deposited film forming apparatus, and FIG. 4B is a schematic diagram of a cross section thereof.

[Explanation of symbols]

 100, 300, 400 Reaction vessel 101, 201, 301, 401 Cylindrical conductive substrate 102, 302, 402 Plate 103, 303 Rotation assisting means 104, 404 Exhaust port 105, 405 Electrode 106, 406 High frequency power supply 107, 407 Matching box 108, 408 Gas release tube 109, 409 Rotating shaft 110, 410 Gear 111, 411 Rotating motor 112 Internal chamber 202 Charge injection blocking layer 203 Photoconductive layer 204 Surface protective layer

Claims (7)

[Claims] 1. A rotary drive means for holding one end of a cylindrical conductive substrate and rotating the cylindrical conductive substrate about a cylindrical axis, wherein the rotary drive means includes a plurality of the cylindrical conductive substrates in a reaction vessel. A plurality of chambers are arranged so as to form an internal chamber that is a space surrounded by the cylindrical conductive substrate by being located on the same circumference, and a means for introducing a source gas into the internal chamber; A means for applying high-frequency power for decomposing the source gas, comprising: supporting one end of the cylindrical conductive substrate on a side not held by the rotation driving means, and assisting rotation. A deposited film forming apparatus, comprising: 2. The deposition apparatus according to claim 1, wherein a plate is provided on one surface of the internal chamber on a side opposite to the surface on which the rotation driving means is disposed, and the plate is provided with rotation assisting means. Film forming equipment. 3. The high frequency power frequency is 20 MHz to 4 MHz.
3. The deposited film forming apparatus according to claim 1, wherein the frequency is 50 MHz. 4. The deposition film forming apparatus according to claim 1, wherein a material of the rotation assisting means is a ceramic material or a metal-based solid lubricating composite material. 5. The material of the plate is Al, Ti, Cr,
Fe, Ni and metals selected from the group consisting of Co, or an alloy thereof, or alumina (Al ₂ O ₃₎ deposited film forming apparatus according to any one of claims 2-4 consisting of. 6. At least a surface of the plate on the inner chamber side is made of alumina (Al ₂ O ₃ ), Al, Ti, or C.
The deposition film forming apparatus according to any one of claims 2 to 4, wherein the surface is roughened by thermal spraying using a metal material selected from the group consisting of r and Ni. 7. The method according to claim 1, wherein the cylindrical conductive substrate is rotated by a rotation driving means while rotating the cylindrical conductive substrate over the entire circumference of the cylindrical conductive substrate. A method for forming a deposited film, comprising forming a deposited film.