JP2000077339A - Deposited film formation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a deposited film efficiently, inexpensively, and safely by installing a substrate in a reaction container that is partially made of an insulation member, setting the pressure in the reaction container to a specific reduced pressure, introducing a discharge power, forming the deposited film, and then eliminating a byproduct adhering to the inner wall of the reaction container. SOLUTION: A wall surface 107 of a reaction container 114 that is partially made of an insulation material and a cylindrical substrate 109 are installed on a bottom surface 108 of the reaction container 114, the reaction container 114 is connected to a deposition film formation device 101, the inside of a reaction space 106 is evacuated, the pressure of the inside of the reaction container 114 is reduced to 10 Pa or less, and a feed gas is introduced into the reaction space 106. Then, a specific high-frequency power is supplied from a high-frequency power supply 104 via a matching box 105. Then, after a deposition film is formed, the reaction container 114 is removed from the deposited film formation device 101, the cylindrical substrate 109 is taken out of the reaction container 114, further the wall surface 107, a material supply means 115, and the like are removed from the reaction container 114, and a byproduct being deposited on each surface is eliminated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a deposited film, which is particularly suitable as a semiconductor element such as an electrophotographic light receiving member, a solar cell, an image input line sensor, an imaging device, and a TFT, on a substrate by a plasma CVD method. It relates to a method of forming.

[0002]

2. Description of the Related Art As one method of forming a deposited film, a CVD method using low-temperature plasma has been spotlighted. In this method, the inside of the reaction vessel is depressurized to a high vacuum, the source gas is introduced into the reaction vessel, and then discharge power is applied to decompose the source gas by glow discharge. A method for forming a deposited film, which is applied, for example, to the formation of an amorphous silicon film.

An amorphous silicon film formed by this method using silane gas (SiH ₄ ) as a film forming material gas has relatively few localized levels in the forbidden band of amorphous silicon, and valence electrons can be controlled by doping impurities. It is possible to obtain an amorphous silicon electrophotographic photoreceptor having excellent characteristics, and studies have been continued.

Japanese Patent Publication No. 60-35059 discloses a light receiving member for electrophotography in which hydrogenated amorphous silicon is applied to a photoconductive portion.

Further, Japanese Patent Application Laid-Open No. Sho 59-142839 discloses that
A method of removing by-products generated on the inner wall of the reaction vessel by dry etching when forming such a deposited film is disclosed.

In Japanese Patent Application Laid-Open No. 62-218570,
A method of removing by-products generated on the inner wall of a reaction vessel when forming such a deposited film by using a detachable cassette is disclosed.

[0007]

SUMMARY OF THE INVENTION The present inventor has been studying a method of forming a deposited film having higher production efficiency in the above-described method of forming a deposited film.

Usually, when a deposited film is formed on a substrate placed in a reaction vessel, by-products adhere to the inner wall of the reaction vessel. In general, these by-products easily peel off from the inner wall, adhere to the substrate, contaminate the substrate, and often cause serious defects in the deposited film. Therefore, it is desirable that after forming the deposited film, by-products attached to the inner wall of the reaction vessel be removed, and then a new substrate be placed in the reaction vessel to form a deposited film on the substrate. Becomes

The by-products adhering to the inner walls of these reaction vessels often become powders generally called polysilanes.
This polysilane burns easily in the atmosphere, so it must be handled with care.

Therefore, as a method for removing by-products adhered to the inner wall of the reaction vessel, a so-called dry etching method for gasifying and removing by-products with a halogen compound such as carbon tetrafluoride or chlorine trifluoride is used. However, after forming the deposited film on the substrate, after performing the dry etching step to remove by-products in the reaction vessel after removing the substrate, there is an advantage that by-products can be safely and easily removed, Due to the long restraint time of the reaction vessel in the dry etching process, there has been a case where productivity may not be sufficiently high.

Another method is to cover the inner wall of a reaction vessel with a removable cassette, form a deposited film on a substrate, remove the cassette from the reaction vessel, and remove by-products attached to the cassette surface. There is a method of removing, and this method has an advantage that the restraining time of the reaction vessel is shortened, but when the by-product is polysilane in powder form, handling with extreme care is required. In some cases, there has been a problem that the efficiency is reduced or a facility for enabling a safe removal operation is required, thereby increasing the capital investment. Therefore, as one method of improving the safety by making the adhered substance adhering to the surface of the cassette not a powder but a film, there is a method of heating the cassette. However, since it is necessary to provide a heating mechanism for heating the cassette in the reaction vessel, an additional restriction is added to the configuration of the film forming apparatus, and the reaction conditions are restricted to sufficiently bring out the characteristics of the deposited film. In some cases, or the cost of the film forming apparatus increases.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has as its object to provide a highly safe method without deteriorating the characteristics of a deposited film efficiently and at low cost, and having excellent productivity. To provide a method for forming a deposited film.

[0013]

According to the present invention, there is provided a method for forming a deposited film, comprising the steps of: forming a discharge space for decomposing a raw material gas; A deposition film forming apparatus consisting of a part, a substrate is disposed in the reaction vessel, a source gas and discharge power are introduced into the reaction vessel, and the source gas is decomposed by the discharge power to form a substrate on the substrate. In a deposition film forming method for forming a deposition film, at least a part of the reaction vessel is made of an insulating member, the substrate is installed in the reaction vessel, and the reaction vessel is attached to the deposition film forming apparatus, The pressure inside the reaction vessel was reduced to 10 Pa or less, a discharge power was introduced to form a deposited film on the substrate, the reaction vessel was removed from the deposited film forming apparatus, and then the substrate was taken out of the reaction vessel, Inside the reaction vessel It is characterized by the removal of by-product adhered to.

According to the method for forming a deposited film of the present invention, a deposited film can be efficiently formed at low cost without deteriorating characteristics, and the features of this method are high workability and safety and high productivity. It is excellent.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, liquid honing and liquid etching can be employed as a method for removing the by-product.

Hereinafter, the present invention will be described in more detail.

As a preferred conventional method for forming a deposited film for efficiently using a reaction vessel and increasing the productivity, as described in the above-mentioned Japanese Patent Application Laid-Open No. 62-218570, for example, Is removed with a removable cassette, and by-products are removed together with the cassette. However, using this method requires a method for removing by-products with high safety and efficiency as described above. .

Therefore, the present inventors not only cover the inner wall of the reaction vessel with a detachable member, but also make the by-products adhering to the member into a film-like form instead of a powdery form that easily burns, and It does not cause side effects such as the formation of a film with high internal stress and easy peeling, or the provision of an extra mechanism in the reaction vessel, which limits the deposition conditions of the deposited film. Without deteriorating the characteristics
As a result of intensive studies on a deposition film forming method capable of efficiently removing by-products, a reaction vessel at least part of which is made of an insulating member was used, and the pressure in the reaction vessel was reduced to 10 Pa or less. By reacting
It has been found that the above-mentioned desired conditions can be realized.

Under the deposition conditions of the deposited film studied by the present inventors, first, when the source gas is decomposed by setting the pressure in the reaction vessel to the above-mentioned range, by-products formed on the inner wall of the reaction vessel are generated. It was found to adhere in the form of a film. As described above, as a method of forming a by-product into a film form, a method of heating the inner wall of the reaction vessel may be mentioned. In this method, in addition to the above-described problem, the inner wall of the reaction vessel is formed during formation of the deposited film. It has been found that the film adhered to the substrate may be peeled off and adhered to the substrate, resulting in a defect in the deposited film on the substrate. In this phenomenon, the molecules that reach the inner wall of the reaction vessel, which would otherwise become powder, promote the surface reaction by the heat energy supplied by heating the reaction vessel, forming it into a film. Therefore, it is considered that internal stress was accumulated in the film-formed by-product, and the film was easily peeled off during formation of the deposited film. On the other hand, in the case of a film-like by-product deposited on the inner wall of the reaction vessel under the above-described conditions of the present invention, a situation in which the by-product is peeled off during formation of the deposited film rarely occurs. Since the molecules generated by decomposition of the gas have little chance of reacting with each other in the gas phase, the molecules reaching the inner wall of the reaction vessel have a low molecular weight. This is probably because the reaction is not required so much that the internal stress does not accumulate much. Further, in the present invention, although the above-mentioned restrictions are added to the film forming conditions of the deposited film, the molecules reaching the substrate have a low molecular weight as described above, so that a surface reaction is not so much required in forming the deposited film. Because of the low internal stress, no deterioration in the characteristics of the deposited film was observed, and in some cases, the effect of obtaining a deposited film having good characteristics was recognized.

Further, by making at least a part of the reaction vessel an insulating member, it is possible to place an electrode outside the reaction vessel, so that the total amount of by-products in the reaction vessel is reduced, Due to the simpler structure of the reaction vessel and improved utilization efficiency of the raw material gas, the work of removing by-products becomes easier, which not only improves the productivity but also causes the by-product film peeling. Also, the probability of occurrence of defects in the deposited film is reduced, and there is also an effect of suppressing the deterioration of the characteristics of the deposited film.

In the present invention, a more stable discharge can be obtained by using 50 to 450 MHz as a preferable range of the frequency of the discharge power for decomposing the raw material gas in order to realize the above-mentioned deposition film forming conditions. As a result, it is possible to realize higher productivity.

Hereinafter, the method for forming a deposited film of the present invention will be described in more detail with reference to the drawings.

FIGS. 1 and 2 are diagrams schematically showing an example of an apparatus for forming a deposited film of an electrophotographic light-receiving member used for carrying out the method of forming a deposited film according to the present invention. The formation of a deposited film using this apparatus can be performed, for example, as follows.

FIG. 1A is a schematic longitudinal sectional view, and FIG. 1B is a schematic transverse sectional view along a cutting line AA 'in FIG. 1A. FIG. 2 is a schematic longitudinal sectional view showing a reaction vessel part of the deposited film forming apparatus.

An exhaust pipe 102 is formed integrally with the deposition film forming apparatus 101, and other components of the exhaust pipe 102 are connected to an exhaust device (not shown). A high-frequency power introduction unit 103 is provided on the deposited film forming apparatus 101, and the high-frequency power output from the high-frequency power supply 104 is supplied to a matching box 105.
Through the high-frequency power supply means 103 to form the film formation space 106
Supplied within.

Reference numeral 107 denotes a wall surface of the reaction vessel 114 at least partly made of an insulating material, and 108 denotes a reaction vessel 11
4 is the bottom surface. In the film forming space 106, a plurality of cylindrical substrates 109 on which a deposited film is formed are arranged in a circumferential shape. Each cylindrical substrate 109 is held by a shaft 110,
Heating is performed by the heating element 111. By driving the motor 112, the shaft 110 is rotated via the reduction gear 113, and a mechanism is provided as necessary so that the cylindrical base 109 rotates around its central axis in the generatrix direction. Reference numeral 115 denotes a source gas supply means for supplying a desired source gas into the film forming space 106. In addition, by installing the second high-frequency power introducing means in the arrangement of the cylindrical substrate 109 as necessary, it is possible to form a more uniform and favorable deposited film over the entire circumference of the cylindrical substrate 109 in the circumferential direction. . Reference numeral 116 denotes a second high-frequency power introduction method, 11
7 is a second high-frequency power supply, and 118 is a second matching box.

The film forming space 106 is formed by installing the reaction vessel 114 shown in FIG. 2 in the deposited film forming apparatus 101 shown in FIG.

In the present invention, the number of the cylindrical substrates 109 is not particularly limited, but the production efficiency is better if a plurality of the cylindrical substrates 109 are provided. However, in general, the cylindrical substrate 1
As the number of 09 increases, the size of the apparatus increases and the required high-frequency power supply capacity increases. Therefore, the number of cylindrical substrates 109 is appropriately determined in consideration of these points.

When a plurality of cylindrical substrates 109 are provided, the arrangement shape of the cylindrical substrates 109 is not particularly limited, but when provided in the same circumferential shape as shown in FIG.
This is a preferable example because the variation in characteristics among the nine types can be reduced.

Alternatively, as shown in FIG. 5, which schematically shows another example of an apparatus for forming a deposited film of a light receiving member for electrophotography using the deposited film forming method of the present invention, a cylindrical substrate 409 is straightened. Also in the case where it is provided on the upper side, variation in characteristics between the cylindrical substrates 409 can be reduced, which is a preferable example.

In the present invention, the effect of the present invention can be obtained regardless of the shape of the reaction space 106 formed by the wall surface 107, but the variation in characteristics between the cylindrical substrates 109 is reduced. In view of this, it is preferable that the shape is similar to the arrangement shape of the cylindrical substrate 109.

As shown in FIG. 1, when the cylindrical substrate 109 is provided in the same circumference, the shape of the wall surface 107 is a cylinder, and a circle of the same circumference formed by arranging the cylindrical substrate 109 ( Hereafter, it is preferable to form a concentric circle with respect to the arrangement circle).

Further, as shown in FIG.
Is provided on a straight line, the wall 407 may have a rectangular parallelepiped shape, and the center axis may be aligned with the cylindrical base 409 as another example. Further, in the case of a rectangular parallelepiped, the wall surface can be formed of a flat plate, which is a preferable example from the viewpoint of reducing the cost of the film forming apparatus.

The material of the wall surfaces 107 and 407 is at least partially made of an insulating material. Specific examples of the insulating material include alumina, titanium dioxide, aluminum nitride, boron nitride, zircon, cordierite, zircon-cordierite, silicon oxide, and beryllium mica ceramics. Of these, alumina and aluminum nitride are particularly preferred because they absorb less high frequency power.

The shapes of the high-frequency power introducing means 103 and 116 are not particularly limited, but the high-frequency power introducing means 116 provided in the film forming space 106 has a curved surface as far as possible from the viewpoint of preventing film peeling. Is preferable, and particularly, a cylindrical shape is preferable. High frequency power supply 10
The high-frequency power supply to 3 and 116 may be performed at one point of high-frequency power supply 103 and 116 or may be performed at a plurality of points.

The surface properties of the high-frequency power supply means 103 and 116 are not particularly limited, but the high-frequency power supply means 116 provided in the film formation space 106 improves the adhesion of the film, prevents the film from peeling, For the purpose of suppressing dust during film formation, it is desirable that the surface is roughened. As a specific degree of the surface roughening, a 10-point average roughness (R
The range of 5 μm or more and 200 μm or less in z) is preferable.

Further, from the viewpoint of improving the adhesion of the film, it is effective that the surface of the high-frequency power introducing means 116 is coated with a ceramic material. Although there is no particular limitation on the specific means of coating, the surface of the high-frequency power introduction hand throw 116 may be coated by, for example, a surface coating method such as a CVD method or thermal spraying. Among the coating methods, thermal spraying is preferable because it is difficult to limit the size and shape of the object to be coated from the viewpoint of cost or the coating object. Specific examples of the ceramic material include alumina, titanium dioxide, aluminum nitride, boron nitride, zircon, cordierite, zircon-cordierite, silicon oxide, and beryllium mica ceramics. The thickness of the ceramic material covering the surface of the high-frequency power introduction means 116 is not particularly limited, and is preferably 1 μm to 10 mm in order to increase durability and uniformity, and from the viewpoint of high-frequency power absorption and manufacturing cost. ５5 mm is more preferable.

Further, by providing a heating or cooling means to the high-frequency power introduction means 116, the adhesion of the film on the surface of the high-frequency power introduction means 116 can be further increased, and the film peeling can be more effectively prevented. In this case, whether to heat or cool the high-frequency power supply means 116 is appropriately determined according to the film material to be deposited and the deposition conditions. Specific heating means is not particularly limited as long as it is a heating element. Specifically, a winding heater of a sheath heater, a plate heater,
Examples include an electric resistance heating element such as a ceramic heater, a heat radiation lamp heating element such as a halogen lamp and an infrared lamp, and a heating element formed by a heat exchange means using a liquid, a gas, or the like as a medium. The specific cooling means is not particularly limited as long as it is a heat absorber. For example, a cooling coil, a cooling plate, a cooling cylinder, or the like that can flow a liquid or a gas as a cooling medium can be used.

In order to prevent the high-frequency power introducing means 103 from excessively rising according to the film material to be deposited and the deposition conditions, a cooling means may be provided in the high-frequency power introducing means 103 as appropriate.

Regarding the shape of the deposited film forming apparatus 101,
The effect of the present invention can be obtained regardless of the shape, and the shape of the film formation space 106 in which the source gas is decomposed may be similar to or different from the shape of the film formation space 106. No problem. However, from the viewpoint of improving the uniformity of the high-frequency power emitted from the high-frequency introducing means 103,
Preferably, it is similar. Further, a shape such as a cylinder or a rectangular parallelepiped is generally used for ease of manufacture.

The material is high-frequency power introducing means 10.
Metals such as Al and stainless steel are desirable from the viewpoint of shielding the power radiation from No. 3 and the mechanical strength.

The number and location of the source gas supply means 115 are not particularly limited, but it is effective to install the source gas supply means 115 so that the source gas is uniformly supplied into the film formation space 106.

When the second high-frequency power supply means 116 is provided as a single unit, the second high-frequency power supply means 116 is preferably installed at the center of the circle of the cylindrical base 109. Further, the second high-frequency power introducing means 11
When there are a plurality of 6, the cylindrical bases 109 are preferably arranged at equal intervals on a concentric circle having the same center as the arrangement circle of the cylindrical bases 109.

The supply of the high-frequency power to the high-frequency power supply means 103 and the second high-frequency power supply means 116 is performed by passing the high-frequency power supply 104 through the matching box 105 and then branching the power supply path. 103,
It is also possible to supply power to the second high-frequency power introducing means 116. However, in terms of controllability, FIG.
Two independent power sources 104 and 117 as shown
It is preferable that the power can be independently controlled by manual throwing such as using the matching boxes 105 and 118. In this case, as described above, the reaction space 106
An oscillating source of high-frequency power introduced from the high-frequency power introducing means 103 provided outside and a second high-frequency power introducing means 11
It is further preferable that the oscillation sources of the high-frequency power introduced from 6 are the same.

The formation of a deposited film using such an apparatus is as follows.
For example, it is performed as follows.

First, the wall 107 and the cylindrical substrate 109 are set on the bottom surface 108, the reaction vessel 114 is connected to the deposition film forming apparatus 101, and the exhaust pipe 102 is exhausted by an exhaust device (not shown).
To exhaust the inside of the reaction space 106. Subsequently, the cylindrical body 109 is heated and controlled to a predetermined temperature by the heating element 111.

When the temperature of the cylindrical substrate 109 reaches a predetermined temperature, the raw material gas is introduced into the reaction space 106 via the raw material gas supply means 115. After confirming that the flow rate of the raw material gas has reached the set flow rate and that the pressure in the reaction space 106 has been stabilized, predetermined high-frequency power is supplied from the high-frequency power supply 104 to the high-frequency power introduction unit 103 via the matching box 105. Depending on the supplied high frequency power,
A glow discharge occurs in the reaction space 106, and the source gas is excited and dissociated to form a deposited film on the cylindrical substrate 109.

After the desired film thickness is formed, the supply of the high-frequency power is stopped, the supply of the source gas is stopped, and the formation of the deposited film is completed. When forming a multi-layered deposited film, the same operation is repeated a plurality of times. In this case, between the respective layers, the discharge is completely stopped once when the formation of one layer is completed as described above, and the discharge is caused again after the settings are changed to the gas flow rate and the pressure of the next layer. The formation of the next layer may be carried out, or a plurality of layers may be continuously formed by gradually changing the gas flow rate, pressure, and high-frequency power to the set values of the next layer within a certain period of time after the formation of one layer. It may be formed.

During the formation of the deposited film, the rotating shaft 11
Alternatively, the cylindrical base 109 may be rotated at a predetermined speed by the motor 112 via the motor.

Further, when the second high-frequency power introducing means 116 is used, two independent high-frequency power controls are required in the apparatus shown in FIG. After setting the power introduced from the introduction means 103 to a predetermined value, the second high-frequency power introduction means 1
The power introduced from 16 may be set to a predetermined value, or the reverse procedure may be used. Further, the power supplied from the high-frequency power supply means 103 and the power supplied from the second high-frequency power supply means 116 may be simultaneously set to a predetermined value.

After the formation of the deposited film, the reaction vessel 114 is removed from the deposited film forming apparatus 101, the cylindrical substrate 109 is taken out of the reaction vessel 114, and the wall surface 107 and the raw material gas supply means 115 are removed from the reaction vessel 114. By-products deposited on the surface of the substrate are removed.

The method of removing by-products is not particularly limited. However, since it is possible to treat a large amount and is excellent in productivity, a liquid honing method using glass beads or the like, sodium hydroxide, hydrofluoric acid, nitric acid, etc. A wet etching method using a diluted solution of the above is mentioned as a preferable processing method.

By using the present invention, it is possible to form an a-Si electrophotographic light receiving member as shown in FIG. 3, for example.

The light receiving member 2 for electrophotography shown in FIG.
In the reference numeral 00, a photoconductive layer 202 made of a-Si: H, X and having photoconductivity is provided on a base 201.

FIG. 3 (b) shows an electrophotographic light-receiving member 2 for electrophotography.
Reference numeral 00 denotes a photoconductive layer 202 made of a, -Si: H, X and having photoconductivity, and an amorphous silicon-based surface layer 203 on a substrate 201.

The light receiving member 2 for electrophotography shown in FIG.
Reference numeral 00 denotes a photoconductive layer 202 made of a-Si: H, X and having photoconductivity, an amorphous silicon-based surface layer 203, and an amorphous silicon-based charge injection blocking layer 204 formed on a substrate 201. I have.

The light receiving member 2 for electrophotography shown in FIG.
No. 00 has a photoconductive layer 202 provided on a base 201. The photoconductive layer 202 includes a charge transport layer 206 and a charge generation layer 205 made of a-Si: H, X, and an amorphous silicon-based surface layer 203 is provided thereon.

[Experimental Examples] Hereinafter, the present invention will be described in more detail with reference to experimental examples. (Experimental Example 1) In the deposition film forming apparatus shown in FIG. 1, an a-Si film was formed on the cylindrical substrate 109 according to the following film forming conditions by using an aluminum cylindrical substrate 109 having a diameter of 80 mm. Filmed.

SiH4: 100 sccm H2: 100 sccm Substrate temperature: 230 ° C. High frequency power: 100 MHz-200 W Film thickness: 5 μm Internal pressure: as shown in Table 1.

After the film formation, the shape of the by-product adhering inside the film formation space 106 of the deposition film forming apparatus 101 was observed. Table 1 shows the results.

As can be seen from Table 1, it was confirmed that the deposit on the wall surface in the film formation space 106 of the reaction vessel became a film under the conditions of 10 Pa or less in the film formation space 106 of the reaction vessel.

[0062]

[Table 1] (Experimental example 2) In Experimental example 1, 50 MHz, 80 MH
z, 200 MHz, using 450 MHz high frequency power,
An a-Si film was formed on the cylindrical substrate 109 in the same manner as in Experimental Example 1 except that the internal pressure was set to 5 Pa and 10 Pa, respectively, and then adhered inside the film forming space 106 of the deposition film forming apparatus 101. The shape of the by-product was observed.

As a result, at any frequency of the high-frequency power, the by-product had a substantially film shape under the condition of the internal pressure of 10 Pa, and the film formed under the condition of the internal pressure of 5 Pa.

[0064]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. (Embodiment 1) In the deposited film forming apparatus shown in FIG. 1, an aluminum cylindrical substrate 109 having a diameter of 80 mm and an alumina inner wall 107 were placed in a reaction vessel 114, and then the reaction vessel 114 was placed in the deposited film forming apparatus 101. Then, an a-Si film is formed on the cylindrical substrate 109 according to the film forming conditions shown in Table 2 to form an electrophotographic light-receiving member having a layer configuration shown in FIG. Deposition film forming device 1
01, the cylindrical substrate 109 is removed from the reaction vessel 114, the inner wall 107 is removed, and the film-like by-product adhering to the inner wall 107 and the bottom surface 108 of the reaction vessel is replaced with an aqueous solution of sodium hydroxide. To remove.

[Table 2] (Comparative Example 1) In the deposited film forming apparatus shown in FIG.
An electrophotographic light-receiving member was formed in the same manner as in Example 1, except that the inner surface of the reaction vessel 114 was heated by blowing hot air at 0 ° C., and the internal pressure at the time of forming each layer was set to 15 Pa.
Film-like by-products adhering to the inner wall 107 and the bottom surface 108 of the reaction vessel were removed in the same manner as in Example 1.

The light receiving member for electrophotography prepared in Example 1 and Comparative Example 1 was evaluated by the following method.

Each light receiving member for electrophotography was set in an electrophotographic apparatus (NP6250 manufactured by Canon Inc. modified for experiments), and a test sheet solid black manufactured by Canon Inc. (part number: FY9-9073-000) was used. Was placed on a platen, and the number of white spots having a diameter of 0.2 mm or more within the same area of the copy image obtained when copying was examined, and the number of white spots of each electrophotographic light receiving member was compared. As a result, the electrophotographic light-receiving member of Example 1 had a small number of white dots of 0.27 as compared with the number of white dots of the electrophotographic light-receiving member of Comparative Example 1, which was excellent in image quality. . (Example 2) A film-like by-product adhering to the inner wall 107, the bottom surface 108 of the reaction vessel, and the like was formed after film formation and removal of a light receiving member for electrophotography in the same manner as in Example 1, and glass beads (Toshiba Barotini) It was removed by liquid honing using GB-AC (manufactured by Corporation). (Comparative Example 2) A photoreceptor material for electrophotography was formed and taken out in the same manner as in Example 1 except that the internal pressure at the time of forming each layer was 15 Pa, and then adhered to the inner wall 107 and the bottom surface 108 of the reaction vessel. The powdery by-product was removed manually. (Comparative Example 3) After forming and taking out a light receiving member for electrophotography in the same manner as in Comparative Example 2, the powdery by-product adhering to the inner wall 107, the bottom surface 108 of the reaction vessel, and the like was treated in the same manner as in Example 1. Removed by method.

In Examples 1 and 2 and Comparative Examples 1 and 3, the amount of work (restriction time for performing the removing operation) required to remove by-products was measured.
The work amount of the deposited film forming method of Comparative Example 3 is 0.6, the work amount of the deposited film forming method of Example 2 is 0.35, and the working amount of the deposited film forming method of Comparative Example 3 is 0.35. The working amount in the deposited film forming methods of Comparative Example 1 and Comparative Example 1 was 0.2.

From the above results, it was found that according to the method for forming a deposited film of the present invention, a light receiving member for electrophotography having high productivity and excellent characteristics can be formed. (Embodiment 3) Using the deposited film forming apparatus shown in FIG.
The electrophotographic light-receiving member was formed into a film and removal of by-products was performed in the same manner as in Example 1 except that the film formation conditions shown in FIG.

In Example 3, as in Example 1, the amount of work required to remove the by-products was measured.

Further, the light receiving member for electrophotography prepared in Example 3 was evaluated in the same procedure as in Example 1. As a result, the number of image defects was the same as in the case of Example 1.

From the above results, it was found that according to the method of forming a deposited film of the present invention, a light receiving member for electrophotography having high productivity and excellent characteristics can be formed.

[0072]

[Table 3] (Embodiment 4) In the deposition film forming apparatus shown in FIG. 5, an aluminum cylindrical substrate 409 having a diameter of 80 mm and an inner wall 407 made of aluminum nitride are placed in a reaction vessel 415, and then the reaction vessel 415 is placed in the deposition film forming apparatus. 3C, an a-Si film was formed on the cylindrical substrate 409 in accordance with the film forming conditions shown in Table 4 to form an electrophotographic light-receiving member having a layer structure shown in FIG. Is removed from the deposited film forming apparatus 401, and
The cylindrical substrate 409 was taken out, the inner wall 407 was removed, and a film-like by-product adhering to the inner wall 407 and the bottom surface 408 of the reaction vessel was removed in the same manner as in Example 1.

[Table 4] (Comparative Example 4) In the deposited film forming apparatus shown in FIG.
A photoreceptor member for electrophotography was formed in the same manner as in Example 4 except that the inner surface of the reaction vessel 415 was heated by blowing hot air at 0 ° C. and the internal pressure during film formation of each layer was set to 15 Pa. Then, a film-like by-product adhering to the inner wall 407 and the bottom surface 408 of the reaction vessel was removed in the same manner as in Example 4.

The number of white spots of each of the electrophotographic light-receiving members produced in Example 4 and Comparative Example 4 was compared in the same manner as in Example 1. In contrast to the number of the dots, the number of the white dots of the electrophotographic light-receiving member of Example 4 was as small as 0.22, and the image quality was excellent. (Example 5) A film-like by-product adhering to the inner wall 407, the bottom surface 408 of the reaction vessel and the like was formed in the same manner as in Example 2 after forming and taking out the electrophotographic light-receiving member in the same manner as in Example 4. Removed by method. (Comparative Example 5) An electrophotographic light-receiving member was formed and taken out in the same manner as in Example 4 except that the internal pressure at the time of forming each layer was set to 15 Pa, and then the inner wall 407 and the bottom surface 4 of the reaction vessel were removed.
The powdery by-product adhering to 08 etc. was removed in the same manner as in Comparative Example 2.

In Examples 4 and 5 and Comparative Examples 4 and 5, the amount of work required to remove by-products was measured. The work amount of the deposited film forming method of Example 5 was 0.3, and the work amount of the deposited film forming methods of Example 4 and Comparative Example 4 was 0.3.
It was 2.

From the above results, it was found that according to the method of forming a deposited film of the present invention, a light receiving member for electrophotography having high productivity and excellent characteristics can be formed. Example 6 The same procedure as in Example 3 was carried out except that a light receiving member for electrophotography was formed according to the film forming conditions shown in Table 5 and by-products were removed with a mixed aqueous solution of hydrofluoric acid, nitric acid and acetic acid. According to the method, the electrophotographic light receiving member was formed into a film and by-products were removed.

In Example 6, the amount of work required to remove by-products was measured in the same manner as in Example 3, and the amount of work was the same as in Example 3.

Further, the light receiving member for electrophotography prepared in Example 6 was evaluated in the same procedure as in Example 3. As a result, the number of image defects was the same as in the case of Example 3.

From the above results, it was found that according to the method for forming a deposited film of the present invention, a light receiving member for electrophotography having high productivity and excellent characteristics can be formed.

[0079]

[Table 5]

[0080]

As described above, according to the present invention,
A deposited film can be efficiently formed at low cost without deteriorating characteristics, and a method of forming a deposited film having high workability and safety and excellent productivity can be implemented.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a deposited film forming apparatus according to the present invention, in which (a) is a longitudinal sectional view, and (b) is a transverse sectional view along AA ′ of (a).

FIG. 2 is a schematic vertical sectional view showing a reaction vessel part of the deposited film forming apparatus of the present invention.

FIGS. 3A to 3D are schematic views showing various examples of a layer structure of a light receiving member for electrophotography produced by the method of the present invention. FIGS.

FIGS. 4A and 4B are schematic views showing another example of the deposited film forming apparatus of the present invention, wherein FIG. 4A is a longitudinal sectional view, and FIG. 4B is a transverse sectional view along AA ′ of FIG.

5A and 5B are schematic views showing another example of the deposited film forming apparatus of the present invention, wherein FIG. 5A is a longitudinal sectional view, and FIG. 5B is a transverse sectional view along AA ′ of FIG.

[Sharp sign]

 101, 301, 401 Deposited film forming apparatus 102, 302, 402 Exhaust pipes 103, 303, 403 High frequency power introduction means 104, 304, 404 High frequency power supply 105, 305, 405 Matching box 106, 306, 406 Film formation space 107, 307 , 407 Wall surface of reaction vessel 108, 308, 408 Bottom surface of reaction vessel 109, 309, 409 Cylindrical substrate 110, 310, 410 Shaft 111, 311, 411 Heating element 112, 312, 412 Motor 113, 313, 413 Reduction gear 114 , 314, 415 Reaction vessel 115, 315, 416 Source gas supply means 116 Second high frequency power means 117 Second high frequency power supply 118 Second matching box 200 Electrophotographic light receiving member 201 Base 202 Photoconductive layer 203 Surface layer 204 Charge injection blocking layer 205 the charge generation layer 206 the charge transport layer 414 driving gear

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshiyasu Shirasuna 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Takashi Otsuka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor: Hitoshi Hosoi, Inc. 3-30-2 Shimomaruko, Ota-ku, Tokyo Within Canon Inc. (72) Inventor: Hitoshi Murayama 3-30-2, Shimomaruko, Ota-ku, Tokyo Within Canon Inc. ( 72) Inventor Kazutaka Akiyama 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H068 CA06 CA29 CA33 CA34 CA60 DA23 EA24 EA30 5F045 AA08 AB04 AC01 AC19 AE15 AE17 AF10 BB08 BB15 BB16 BB20 CA13 CA15 CA16 DA52 DP25 DQ10 EB06 EH15

Claims (18)

[Claims] 1. A substrate is disposed in a reaction vessel using a deposition film forming apparatus including a reaction vessel capable of forming a discharge space for decomposing a raw material gas and capable of reducing pressure, and an exhaust unit for exhausting the inside of the reaction vessel. Introducing a source gas and discharge power into the reaction vessel, and decomposing the source gas with the discharge power to form a deposition film on the substrate, wherein at least a part of the reaction vessel is formed. Is made of an insulating member, the substrate is placed in the reaction vessel, the reaction vessel is attached to the deposition film forming apparatus, and the inside of the reaction vessel is 10 P
a, the discharge power is introduced to form a deposited film on the substrate, the reaction vessel is removed from the deposited film forming apparatus, and then the substrate is taken out of the reaction vessel, and the inner wall of the reaction vessel is removed. A method for forming a deposited film, comprising removing a by-product adhered to a substrate. 2. An insulating member constituting at least a part of the reaction vessel is made of alumina, titanium dioxide, aluminum nitride, boron nitride, zircon, cordierite, zircon cordierite, silicon oxide, beryllium mica-based ceramics. 2. The method according to claim 1, wherein the method comprises at least one. 3. The method according to claim 1, wherein a vacuum is maintained in the reaction vessel. 4. The method according to claim 1, wherein an electrode for introducing discharge power into the reaction vessel is provided around the reaction vessel. 5. The method according to claim 4, wherein a plurality of the electrodes are provided. 6. The method according to claim 1, wherein the reaction vessel has a cylindrical shape. 7. The method according to claim 6, wherein the plurality of electrodes are arranged circumferentially so as to surround the reaction vessel. 8. The method according to claim 1, wherein the reaction vessel has a rectangular parallelepiped shape. 9. The method according to claim 8, wherein the plurality of electrodes are arranged in a rectangular shape so as to surround the reaction vessel. 10. The method according to claim 1, wherein the substrate has a cylindrical shape. 11. The method according to claim 1, wherein the substrate is plural. 12. The method according to claim 11, wherein the plurality of substrates are arranged circumferentially. 13. The method according to claim 12, wherein an electrode for introducing discharge power into the reaction vessel is provided inside the circumferentially arranged base. 14. The method according to claim 11, wherein the plurality of substrates are arranged linearly. 15. The method according to claim 1, wherein the pressure inside the reaction vessel is reduced to 5 Pa or less. 16. The method according to claim 1, wherein the frequency of the discharge power introduced into the reaction vessel is 50 MHz to 450 MHz. 17. The method according to claim 1, wherein by-products attached to the inner wall of the reaction vessel are removed by liquid honing. 18. The method according to claim 1, wherein by-products attached to the inner wall of the reaction vessel are removed by liquid etching.