JPH11345779A - Apparatus and method for vacuum treating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and a method for vacuum treating, for simplifying and low cost of a production system by realizing an apparatus and a method for easily, effectively and rapidly attaching and detaching a reaction vessel and an evacuation unit. SOLUTION: This apparatus for vacuum treating for communicating a member for forming an opening provided at a reaction vessel 106 with a member for forming an opening provided at an evacuation means 107 comprises the pressure reducible reaction vessel 106, a means for supplying active gas into the vessel, and the means 107 for reducing the pressure of the vessel 106, in such a manner that the diameter of the opening of the container 106 is different from that of the opening provided at the evacuation means 107.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vacuum processing apparatus used for forming a semiconductor device, an electrophotographic photosensitive member, an image input line sensor, a photographing device, a photovoltaic device, etc., for forming a deposited film, etching and the like. Regarding the processing method. Note that, in the present invention, the vacuum processing refers to performing some processing on an object to be processed in a reaction vessel in a reduced pressure state.

[0002]

2. Description of the Related Art Conventionally, semiconductor devices, electrophotography
Body, image input line sensor, imaging device, photovoltaic
Force devices, other electronic elements, optical elements
Vacuum deposition method, vacuum processing method
Puttering method, ion plating method, thermal CVD
Method, photo CVD method, plasma CVD method, plasma etching
There are many known methods such as
Have been. For example, a plasma CVD method, that is, a raw material
DC or radio frequency or microwave glow discharge of gas
To form a thin deposited film on a substrate by decomposition
Has been put into practical use as a suitable means for forming a deposited film.
For example, hydrogenated amorphous silicon for electrophotography (hereinafter, "a
−Si: H ”), and the like.
Various devices have been proposed for this purpose. Such a deposition
The film forming apparatus and the film forming method are roughly as follows.
You. FIG. 9 shows an RF plug using an RF band frequency as a power source.
Zuma CVD (hereinafter abbreviated as "RF-PCVD")
Film forming apparatus, specifically light receiving member for electrophotography
1 is a schematic configuration diagram illustrating an example of a forming apparatus. In FIG.
The configuration of the forming apparatus shown is as follows. This device is large
Separately, the deposition apparatus 2100 and the source gas supply apparatus 220
0, exhaust device for reducing the pressure inside the reaction vessel 2101
(Not shown). In the deposition device 2100
A cylindrical substrate 2112 and a substrate
Substrate support 2113 with built-in heater for heating, source gas
An introduction pipe 2114 is installed, and a high-frequency matching box is
Box 2115 constitutes a part of the reaction vessel 2101.
Connected to the ground electrode 2111. Cathode electrode 21
11 is insulated from the earth potential by an insulator 2120,
Anode maintained at ground potential through support 2113
A high-frequency voltage is applied between the electrode and the cylindrical base 2112 also serving as an electrode.
It can be applied. The raw material gas supply device 2200 includes:
SiH_Four, GeH_Four, H_Two, CH_Four, B_TwoH₆, PH_ThreeOriginal field
Gas cylinders 2221 to 2226 and valves 2231 to
2236, 2241 to 2246, 2251 to 2256
And mass flow controllers 2211 to 2216
The source gas cylinders are configured via a valve 2260.
Connected to the gas introduction pipe 2114 in the reaction vessel 2101
ing. The formation of a deposited film using this apparatus is as follows, for example.
It can be performed as follows. First, the reaction vessel 2101
A cylindrical base 2112 is installed in the inside, and an exhaust device (not shown)
The inside of the reaction vessel 2101 is evacuated by a (for example, a vacuum pump).
I do. Subsequently, the substrate processing unit built in the substrate support 2113 is processed.
The temperature of the cylindrical substrate 2112 is set to 200 by the heating heater.
The temperature is controlled to a predetermined temperature in the range of from 350C to 350C. For deposition film formation
In order for the raw material gas to flow into the reaction vessel 2101, the gas
Cylinder valves 2231 to 2236, reaction vessel leak
Check that valve 2117 is closed, and
Inlet valves 2241 to 2246, outflow valves 2251 to 2
256, confirm that auxiliary valve 2260 is open
Then, first, the main valve 2118 is opened and the reaction vessel 21 is opened.
01 and the inside of the gas pipe 2116 are exhausted. Next, vacuum gauge
The reading of 2119 is about 7 × 10^-FourAssist when Pa becomes
Close valve 2260 and outflow valves 2251 to 2256
You. After that, each gas is sent from gas cylinders 2222-1226.
Open the valves 2231 to 2236 and introduce
Each gas pressure is set to 2 kg / cm by the heaters 2261 to 2266. ^Two
Adjust to Next, the inflow valves 2241 to 2246 are gradually
Open each gas and send each gas to the mass flow controller 221
Introduced into 1-2216. As described above,
After the preparation is completed, each layer is formed by the following procedure. Cylindrical
When the temperature of the substrate 2112 reaches a predetermined temperature,
And auxiliary bars
The lube 2260 is gradually opened and the gas cylinders 2221 to 222 are opened.
Reaction of predetermined gas from 26 through gas introduction pipe 2114
It is introduced into the container 2101. Next, the mass flow controller
Each raw gas is supplied to a predetermined flow by the heaters 2211 to 2216.
Adjust to the amount. At that time, inside the reaction vessel 2101
The vacuum gauge 2119 is considered so that the pressure becomes a predetermined value.
Then, the opening of the main valve 2118 is adjusted. Internal pressure is stable
Then, a 13.56 MHz RF power supply (not
(Shown) to the desired power, and
And the reaction vessel 21 through the cathode 2111
01, RF power is introduced into
The glow discharge is generated by acting as a mode. This release
Source gas introduced into the reaction vessel by electric energy
Is decomposed, and predetermined silicon is formed on the cylindrical substrate 2112.
This is where the deposited film containing the main component is formed. Desired
After the film thickness is formed, stop supplying RF power and flow out
Close the valve to stop the gas from flowing into the reaction vessel.
Finish the formation. By repeating the same operation several times
Thus, a light receiving layer having a desired multilayer structure is formed. Each
When forming these layers, the outflow valves other than the necessary gas
Needless to say, everything is closed,
Each gas flows into the reaction vessel 2101 and the outflow valve 225.
Residue in the piping from 1-2256 to the reaction vessel 2101
In order to avoid running out, the outflow valves 2251 to 225
6, the auxiliary valve 2260 is opened, and the main
With the lube 2118 fully opened, the system is once evacuated to a high vacuum.
Perform operations as needed. To achieve uniform film formation
During the layer formation, the cylindrical substrate 2112 is
It is rotated at a predetermined speed by a driving device (not shown).
Both are effective. In addition, the gas types and valve operation described above
The work is changed according to the creation conditions of each layer
Needless to say. Such conventional RF band
Film shape by RF plasma CVD method using different frequencies
In addition to forming devices and forming methods, in recent years, high
Plasma CVD using microwave power (hereinafter "VHF-
PCVD ”method) has attracted attention.
The development of various deposited films used has also been actively promoted.
You. This is because the film deposition rate is high in the VHF-PCVD method,
In addition, high quality deposited films can be obtained, resulting in low cost products
And high quality are expected to be achieved at the same time.
It is. For example, JP-A-6-287760 discloses a-
Apparatus and method usable for forming a light receiving member for Si-based electrophotography
A law is disclosed. In addition, a plurality of photoreceptors for electrophotography
As shown in Fig. 4, the material can be formed simultaneously and the productivity is extremely high.
Development of such a deposited film forming apparatus is also underway. FIG.
10A is a schematic sectional view, and FIG. 10B is a cutaway view of FIG.
It is a schematic sectional drawing which follows the disconnection A-A '. Reaction vessel 301
An exhaust pipe 311 is integrally formed on a side surface of the exhaust pipe 311.
The other end of 11 is connected to an exhaust device (not shown). reaction
The deposited film is formed so as to surround the center of the container 301.
So that the six cylindrical substrates 305 are parallel to each other.
Are located. Each cylindrical substrate 305 is
Therefore, it is held and heated by the heating element 307.
It has become. When the motor 309 is driven, the reduction gear 3
The rotation shaft 308 rotates through the shaft 10 and the cylindrical base 305 is rotated.
Began to rotate around its central axis in the bus direction
I have. Film formation space surrounded by six cylindrical substrates 305
306 is supplied with the source gas from the source gas supply unit 312
Is done. VHF power matching from VHF power supply 303
A film formation space from the cathode electrode 302 via the box 304
306. At this time, through the rotation shaft 308
The cylindrical substrate 305 maintained at the source potential
Act as

The formation of a deposited film using such an apparatus can be performed according to the following procedure. First, the cylindrical substrate 305 is set in the reaction vessel 301, and the inside of the reaction vessel 301 is exhausted through the exhaust pipe 311 by an exhaust device (not shown). Subsequently, the cylindrical substrate 3 is heated by the heating element 307.
05 is heated and controlled to a predetermined temperature of about 200 ° C. to 300 ° C. When the temperature of the cylindrical substrate 305 reaches a predetermined temperature, the source gas is introduced into the reaction vessel 301 via the source gas supply means 313. After confirming that the flow rate of the raw material gas has reached the set flow rate and the pressure in the reaction vessel 301 has been stabilized, the matching box 3
A predetermined VHF power is supplied to the cathode electrode 302 via the power supply line 04. As a result, VHF power is introduced between the cathode 302 and the cylindrical substrate 305 also serving as the anode, and a glow discharge occurs in the film forming space 306 surrounded by the cylindrical substrate 305, and the source gas is excited and dissociated. Thus, a deposited film is formed on the cylindrical substrate 305. After the desired film thickness is formed, the supply of the VHF power is stopped, then the supply of the source gas is stopped, 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 is formed. During the formation of the deposited film, the cylindrical substrate 305 is rotated at a predetermined speed by the motor 309 via the rotating shaft 308, so that the deposited film is formed over the entire surface of the cylindrical substrate. Japanese Patent Application Laid-Open No. 8-253865 discloses a technique for simultaneously forming a deposited film on a plurality of substrates by using a plurality of electrodes. It is shown that it can be obtained. Such an apparatus form can be realized by, for example, an apparatus as shown in FIG. FIG. 11A is a schematic longitudinal sectional view, and FIG. 11B is a schematic transverse sectional view. An exhaust port 405 is integrally formed on the upper surface of the reaction vessel 400, and the other end of the exhaust port 405 is connected to an exhaust device (not shown). In the reaction vessel 400, a plurality of cylindrical substrates 401 on which a deposited film is formed are arranged so as to be parallel to each other. Each cylindrical substrate 401 is held by a shaft 406 and is heated by a heating element 407. If necessary, the cylindrical base 401 is rotated by a driving means such as a motor (not shown) via the shaft 406. The VHF power is supplied from the VHF power supply 403 through the matching box 404 to the cathode electrode 402 into the reaction vessel 400. At this time, the cylindrical substrate 401 maintained at the ground potential through the shaft 406 functions as an anode electrode. The source gas is supplied into the reaction vessel 400 by a source gas supply unit (not shown) installed in the reaction vessel 400. Formation of a deposited film using such an apparatus can be performed by the same procedure as that of the deposited film forming apparatus shown in FIG.

[0004]

Although a deposited film is formed by the above-described conventional method and apparatus, there is room for further contrivance in consideration of actual production. Today, there are a wide variety of products utilizing such a deposited film forming apparatus and a deposited film forming method, and the deposited film forming apparatus to be used is often different depending on each product. This is because a deposited film forming apparatus using the most suitable size, material, and the like for each product is used. For example, in the production of an electrophotographic photoreceptor, the size of a deposited film forming apparatus, more specifically, the dimensions of the deposited film forming apparatus, particularly the dimensions of the cathode, may be changed according to the diameter of the electrophotographic photoreceptor to be produced.

[0005] Under such circumstances, when the reaction vessel and the exhaust system are substantially integrated, and when a different product is newly produced, it is necessary to add a new production line including the exhaust system. It is necessary to remodel the conventional production line and replace the new reaction vessel with the conventional reaction vessel.
Adding a new production line requires enormous capital investment, and when replacing a new reaction vessel with a conventional one, the production line cannot be operated during the remodeling, resulting in reduced production efficiency. I will.

Furthermore, when a conventional product and a new product are produced in parallel, each production line has a separate production line. Even if the required production number changes, the production line number ratio is immediately changed. Cannot be adjusted. From such a point, it is not possible to connect the reaction container corresponding to a required product to the exhaust device and perform the deposition film forming process according to the production plan by configuring the deposition film forming apparatus so that the reaction container and the exhaust device can be separated. It greatly enhances the flexibility in production, and can improve production efficiency and reduce production costs. In such an apparatus configuration, when the reaction container is movable, the substrate can be placed in the reaction container by moving the reaction container to a separately provided stage for substrate installation. This eliminates the need for a complicated substrate transport device for transporting and installing the substrate to each reaction container as in the case of fixing the reaction container.
The production system can be simplified.

However, there is still room for improvement in a deposited film forming process using such a deposited film forming apparatus and method. It is a current problem to overcome these points and to fully exploit the advantages of the deposited film forming apparatus and the deposited film forming method. One of the issues to be improved is to realize an apparatus configuration and a processing method that can easily, reliably, and quickly connect a reaction vessel and an exhaust device. In order to connect the reaction vessel and the exhaust device, it is of course possible to accurately position, move and connect the reaction vessel by a mechanical connection system, but in this case a large-scale connection system is required It will be. On the other hand, when an operator moves and connects the reaction container, the large-scale connection system as described above becomes unnecessary, and the production system can be simplified. However, in this method, when the reaction vessel is sufficiently small and light enough in weight, accurate positioning and connection can be easily performed, while the reaction vessel is relatively large, In the case of relatively heavy, accurate positioning, connection always easy, reliable,
It becomes difficult to do it quickly. Therefore, realizing the structure of the deposited film forming apparatus and the method of forming the deposited film, which can easily position the reaction vessel and connect to the exhaust device, can simplify the production system and reduce the cost. It is an important point in this, and early realization was desired. Further, there is a problem that the vacuum performance is reduced between the connection portion between the reaction vessel and the exhaust device. This is because active species excited by plasma discharge are deposited at the connection part. If active species are deposited unevenly at the connection part, the adhesion of the connection part is reduced and a high degree of vacuum is maintained. It becomes difficult to do. Alternatively, if the reaction vessel is an etching device, the activated etching gas may etch the upstream connection. The etched connection portion has poor flatness, the adhesion of the connection portion is reduced, and it is difficult to maintain a high degree of vacuum. Therefore, it is also a major current problem to prevent the activated gas from impairing the flatness of the connecting portion between the reaction vessel and the exhaust device that are in close contact with each other, and to maintain a high degree of vacuum in the reaction vessel.

Accordingly, the present invention solves the above-mentioned problems, and realizes a vacuum processing apparatus configuration and a vacuum processing method capable of easily, reliably and quickly attaching and detaching a reaction vessel and an exhaust device, thereby simplifying a production system. It is an object of the present invention to provide a vacuum processing apparatus and a vacuum processing method that can achieve reduction in cost and cost.

[0009]

According to the present invention, in order to achieve the above object, a vacuum processing apparatus and a vacuum processing method are configured as follows. That is, the vacuum processing apparatus of the present invention, a reaction vessel capable of decompression,
A means for supplying an active gas into the reaction vessel, an exhaust means for depressurizing the reaction vessel, a member forming an opening provided in the reaction vessel, and a means provided for the exhaust means In a vacuum processing apparatus in which a member forming an opening communicates with each other, an opening diameter of the opening provided in the reaction vessel is smaller than an opening diameter of the opening provided in the exhaust means. Further, in the vacuum processing method of the present invention, the member forming the opening provided in the reaction vessel that can be decompressed and the member forming the opening provided in the exhaust unit communicate with each other, and the exhaust unit is supplied into the reaction container. Vacuum processing method for evacuating the reactive gas,
The opening diameter of the opening of the member forming the opening provided in the reaction vessel is the opening diameter of the opening of the member forming the opening provided in the exhaust means. Further, the present invention provides a reaction vessel capable of reducing pressure,
A vacuum processing apparatus having an exhaust unit for reducing the pressure through an opening on the reaction vessel side, or a vacuum processing method in which the exhaust unit reduces the pressure of the reaction vessel capable of reducing the pressure through the opening on the reaction container side, The opening diameter on the reaction vessel side is different from the opening diameter on the exhaust means side connected to the opening on the reaction vessel side. And these inventions are characterized in that the member forming the opening provided in the reaction vessel is cylindrical. These inventions are characterized in that the member forming the opening provided in the exhaust means has a cylindrical shape. Further, these inventions are characterized in that the opening provided in the exhaust means is provided in an outer frame of the exhaust means. These inventions are characterized in that the member forming the opening provided in the reaction vessel has a flange. Further, in these inventions, the member forming the opening provided in the exhaust means has a flange. These inventions are characterized in that the vacuum processing apparatus is a deposited film forming means for forming a deposited film on a substrate housed in the reaction vessel. These inventions are characterized in that the deposited film forming means or the deposited film forming step is a deposited film forming means by a plasma CVD method. Also,
In these inventions, the means for forming a deposited film by the plasma CVD method or the step of forming the deposited film has a frequency of 50 to 4 times.
It is characterized by having a means for applying a high frequency power of 50 MHz. Further, the vacuum processing method of the present invention is characterized in that the vacuum processing step is an electrophotographic photosensitive member forming step. Further, the present invention provides a vacuum processing apparatus having a reaction vessel capable of depressurization and an exhaust means for reducing the pressure through an opening on the reaction vessel side, or a reaction vessel capable of depressurizing the exhaust means on the reaction vessel side. In a vacuum processing method in which the pressure is reduced through an opening, an opening diameter on the reaction container side is smaller than an opening diameter on the exhaust unit connected to the opening on the reaction container side. Further, the present invention provides a vacuum processing apparatus having a reaction vessel capable of depressurization and an exhaust means for reducing the pressure through an opening on the reaction vessel side, or a reaction vessel capable of depressurizing the exhaust means on the reaction vessel side. In the vacuum processing method of reducing the pressure through an opening, the opening diameter on the reaction vessel side is configured to be different from the opening diameter on the exhaust unit side connected to the opening on the reaction vessel side, and the inside of the reaction vessel is It is characterized in that an active gas is supplied.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that the connecting portion between the reaction vessel and the exhaust device constituting the vacuum vessel of the present invention is constructed as described above. Thus, connection or disconnection of the reaction vessel and the exhaust device can be performed extremely easily, reliably, and quickly. According to the present invention, there is provided at least a reaction vessel capable of reducing pressure, and an exhaust means for exhausting gas introduced into the reaction vessel, wherein the reaction vessel is detachable from the exhaust means by a connection portion. In the apparatus and its vacuum processing method, the attachment / detachment of the reaction container to / from the exhaust means can be performed easily, reliably, and quickly, and the production system can be simplified and the cost can be reduced. Further, the vacuum processing apparatus and the vacuum processing method of the present invention can be preferably used as, for example, a deposited film forming apparatus and a deposited film forming method.

Regarding such an embodiment of the present invention,
Details will be described below. In the vacuum treatment of the present invention, first,
The vacuum processing apparatus has a reaction container and an exhaust unit, and the reaction container and the exhaust unit each have a flange having an opening,
The reaction vessel and the exhaust means communicate with each other through the opening, are attached and detached, and the opening diameter on the reaction vessel side is different from the opening diameter on the exhaust means side. With such a configuration,
When connecting the reaction vessel to the exhaust means, even if the central axis of the reaction vessel side opening and the central axis of the exhaust means side opening are displaced to some extent at the time of connection, since the opening area of the smaller opening diameter does not decrease, The exhaust conductance when depressurizing the inside of the reaction vessel does not substantially decrease. For this reason, when connecting the reaction vessel and the exhaust means, strict positioning is not required, and the connection can be easily and quickly performed.

Further, the vacuum processing apparatus of the present invention has a configuration in which the opening diameter on the side of the reaction vessel is smaller than the opening diameter on the side of the exhaust means, so that the connection operation of the reaction vessels is further facilitated. On the other hand, for example, when the opening diameter on the reaction vessel side is larger than the opening diameter on the exhaust means side, a part of the exhaust means side flange surface is configured to enter the reaction vessel side opening area. When used as a deposition film forming apparatus for depositing a film using active species generated in the reaction vessel, the active means generated in the reaction vessel causes the exhaust means side flange surface to enter the opening area. There is a case where a film is attached to a part and the vacuum performance is reduced. Alternatively, when a vacuum seal is provided between the exhaust means side flange and the reaction vessel side flange to make contact with each other, active species reach not only the part of the exhaust means side flange entering the opening area but also the vacuum seal. . The active species reaching the vacuum seal lowers the durability of the vacuum seal and lowers the vacuum performance. For this reason, in a configuration in which the opening diameter of the flange on the reaction vessel side is larger than the opening diameter of the flange on the exhaust means side, it may be necessary to frequently remove the film attached to the flange surface.

On the other hand, in the present invention, since the opening diameter of the flange on the reaction vessel side is smaller than the opening diameter of the flange on the exhaust means side, even if active species hits the flange surface on the exhaust means side, film adhesion occurs. In addition, the above-described operation of removing the adhered film is unnecessary, and the connection operation can be performed reliably and efficiently. From the viewpoint of such film adhesion, a vacuum processing apparatus and a vacuum processing method are used as a deposited film forming apparatus and a deposited film forming method, so that the opening diameter on the reaction vessel side is smaller than the opening diameter on the exhaust unit side. Has a particularly pronounced effect. Furthermore, the configuration in which the opening diameter of the flange on the reaction vessel side is smaller than the opening diameter of the flange on the exhaust means side,
Among the deposited film forming apparatus and the deposited film forming method, the present invention is more effective particularly in the deposited film forming apparatus and the deposited film forming method using the plasma CVD method. More specifically, in a deposited film forming apparatus and a deposited film forming method using a plasma CVD method, active species may be generated in an exhaust pipe under the influence of plasma. Then, when active species are generated in the exhaust pipe, film adhesion in the exhaust pipe becomes more prominent. On the other hand, as disclosed in the present invention, if the opening diameter of the flange on the reaction vessel side is smaller than the opening diameter of the flange on the exhaust means side, the above-mentioned film deposition apparatus can be used even in a deposition film forming apparatus using a plasma CVD method. Can be prevented, and high workability is maintained.
As described above, in the deposited film forming apparatus and the deposited film forming method using the plasma CVD method, it is very effective that the opening diameter of the flange on the reaction vessel side is smaller than the opening diameter of the flange on the exhaust means side. is there.

In such a deposited film forming apparatus and a deposited film forming method using the plasma CVD method, when a plasma is formed by using a high-frequency power having a frequency of 50 to 450 MHz, the opening diameter of the flange on the side of the reaction vessel. Is smaller than the opening diameter of the flange on the side of the exhaust means. Because the frequency is 50-450
This is because, when high-frequency power of MHz is used, film adhesion to the exhaust pipe is particularly remarkable. Frequency 50-450MHz
The reason why the film adhesion becomes particularly noticeable when using high-frequency power is not known at present, but in this frequency band, the amount of high-frequency power leaking to the exhaust pipe side is large,
It is presumed that a large amount of active species is generated on the exhaust pipe side by the leakage power. Further, even when the vacuum processing apparatus and method of the present invention are used as an electrophotographic photoreceptor forming apparatus and method, more remarkable effects can be obtained. In the production of electrophotographic photoreceptors, when a deposited film is formed on a substrate, dust and the like fly off and adhere to a substrate, and the incidence of defects in the deposited film depends on the performance and productivity of the electrophotographic photoreceptor. Is extremely involved. If a defect occurs in an electrophotographic photoreceptor, it is extremely difficult to remove that part and commercialize another part or repair it.For example, if a defect is found somewhere in a large area film deposition area, If it occurs, all other film deposition regions where no defect occurs cannot be utilized.

In addition, when the connection between the reaction vessel and the exhaust section is not made smoothly, if the connection is made many times, dust is generated in the reaction vessel due to the vibration at the time of connection and adheres to the substrate. , That is, the possibility that defects occur.
According to the present invention, the connection is smoothly performed,
Such a possibility is reduced, and the performance and productivity of the electrophotographic photoreceptor are improved. In forming an electrophotographic photoreceptor, since a relatively thick deposited film having a thickness of several μm to several tens μm is formed substantially continuously on the substrate, the amount of the deposited film adhered to the exhaust pipe wall in one cycle of the process is reduced. Many. Therefore, in such an electrophotographic photoreceptor forming apparatus and method, it is more effective that the opening diameter on the reaction vessel side is smaller than the opening diameter on the exhaust means side.

Hereinafter, the specific structure will be described in more detail. FIG. 1 is a schematic view of an example of a vacuum processing apparatus that can be used in the present invention. In FIG. 1, reference numeral 101 denotes a movable reaction vessel portion, which includes a reaction vessel 106, a vacuum sealing valve 108 provided as necessary, and a reaction vessel side connection flange 1.
04 and a carriage 113 which is a movable means on which the reaction vessel 106 is mounted and which can move the same. Also, 102
Denotes an exhaust unit, which comprises an exhaust unit 107, a vacuum sealing valve 109 provided as needed, and an exhaust unit side connection flange 105. 103 is a connection part for connecting the reaction vessel part 101 and the exhaust part 102.

FIG. 2 is a schematic diagram for more specifically explaining the connecting portion 103 in FIG. Connection part 10
Reference numeral 3 denotes a reaction vessel side connection flange 104, an exhaust means side connection flange 105, and a vacuum sealing material 110. The reaction vessel side connection flange 104 and the exhaust means side connection flange 105 are provided on the exhaust means side connection flange. The contact is made via the provided vacuum seal material 110. The opening diameter r of the opening 111 of the reaction vessel side connection flange 104 is different from the opening diameter R of the opening 112 of the exhaust means side connection flange 105.
4 has a configuration in which the opening diameter r of the opening 111 is smaller than the opening diameter R of the opening 112 of the exhaust means side connection flange 105.

With respect to the configuration inside the reaction vessel 106, for example, the configuration shown in FIG. 3 can be used. FIG.
FIG. 3 is a schematic view of a reaction vessel section of a deposited film forming apparatus for forming a photoconductor for electrophotography. FIG. 3A is a schematic cross-sectional view, and FIG. 3B is a schematic cross-sectional view along a cutting line AA ′ in FIG. An exhaust pipe 511 is formed on a side surface of the reaction vessel 501, and the other end of the exhaust pipe 511 is connected to the vacuum sealing valve 108 in FIG. The opening of the exhaust pipe is provided with a conductive mesh (not shown) in order to prevent the influence of the high frequency power introduced into the reaction vessel from reaching the exhaust means. The cylindrical substrates 505 on which the deposited films are formed are arranged at equal intervals in parallel on the same circumference. The base 505 is held by a rotating shaft 508 and a motor 509 is provided.
Is driven, the rotating shaft 508 is rotated via the reduction gear 510, and the cylindrical base 505 rotates around its central axis in the generatrix direction. Also, the cylindrical substrate 50
5 can be heated by a heating element 507.

The high-frequency power output from the high-frequency power supply 503 is supplied from the cathode electrode 502 to the reaction vessel 501 serving as a film forming space via the matching box 504 and the high-frequency power supply cable 515. A cathode electrode 506 is also provided within the circle of the cylindrical base 505, and the high-frequency power output from the high-frequency power supply 514 is supplied to the matching box 513 and the high-frequency power supply cable 51.
5, is supplied from the cathode electrode 506 into the reaction vessel 501. Source gas supply means 5 is provided in reaction vessel 501.
12 is provided to supply a desired source gas into the reaction vessel 501.

A vacuum processing method using such a vacuum processing apparatus, for example, when a deposition film forming reaction container for forming an electrophotographic photosensitive member shown in FIG. It can be carried out. First, the movable reaction vessel part 101 is separated from the exhaust part 102, and the cylindrical base 505 is placed inside the reaction vessel 501 in a state where the connection flange 104 is connected to the exhaust device at the time of substrate placement on a separately provided substrate placement stage (not shown). Installed in continue,
The inside of the reaction vessel 501 is exhausted through the exhaust pipe 511 by the exhaust device for substrate installation. At this time, it goes without saying that the vacuum sealing valve 108 is opened. After the inside of the reaction vessel 501 is evacuated to a desired pressure, the heating element 50
7 heats and controls the cylindrical substrate 505 to a predetermined temperature.

Next, after closing the vacuum sealing valve 108, the connecting flange 104 is separated from the exhaust device for installing the base. Subsequently, the movable reaction vessel unit 101 is moved to a place where the exhaust unit 102 is installed, and the connection flange 104 is brought into contact with the exhaust unit side connection flange 105 via the vacuum seal material 110 to be connected thereto. After the connection, if necessary, the connecting portion 103 is fixed by a fixing means such as a screw or a clamp. After confirming that the movable reaction vessel section 101 is connected to the exhaust section 102, first, the exhaust section side vacuum sealing valve 109 is opened, and the inside of the pipe on the exhaust means 107 side is exhausted from the reaction vessel side vacuum sealing valve 108. The gas is evacuated by means 107 and then the reaction vessel side vacuum sealing valve 10
8 is opened and the inside of the reaction vessel 106 is exhausted.

The process of disposing the substrate in the reaction vessel 106, the process of moving the reaction vessel 101, the reaction vessel 101
In the process of connecting to the exhaust unit 102, in addition to the above-described procedure, for example, after installing the base, the reaction container unit 101 is moved without exhausting the inside of the reaction container 106, It is also possible to use a procedure such as moving the reaction vessel section 101 with a desired gas introduced into the vessel 106 at a predetermined pressure. Further, after the reaction vessel section 101 is connected to the exhaust section 102, a base may be installed in the reaction vessel 106. In the other procedure, the reaction vessel 101
May be connected to the exhaust unit 102 so that the inside of the reaction vessel 106 can be vacuum-processed by the time the vacuum processing step is started. The specific procedure takes into account work efficiency, productivity, etc. in each production step. To decide.

After the substrate is placed in the reaction vessel 106 and the inside of the reaction vessel 106 is exhausted by the exhaust means 107, the cylindrical body 505 is heated to a predetermined temperature by the heating element 507, if necessary. ·Control. When the temperature of the cylindrical substrate 505 reaches a predetermined temperature, the source gas is introduced into the reaction vessel 501 via the source gas supply means 512. After confirming that the flow rate of the raw material gas has reached the set flow rate and the pressure in the reaction vessel 501 has been stabilized, the matching boxes 504 and 513 are output from the high-frequency power supplies 503 and 514.
A predetermined high-frequency power is supplied to the cathode electrodes 502 and 506 via the. A glow discharge is generated in the reaction vessel 501 by the supplied high-frequency power, and the source gas is excited and dissociated to form a deposited film on the cylindrical substrate 505.

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 each layer, the discharge is completely stopped once 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 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, if necessary, the rotating shaft 50
The cylindrical base 505 may be rotated at a predetermined speed by the motor 509 via the motor 8. After the deposition film forming step is completed in this way, the source gas in the reaction vessel 106 is sufficiently purged, preferably replaced with an inert gas, and then the vacuum sealing valves 108 and 109 are closed. Subsequently, when the connection unit 103 is disconnected and the reaction container unit 101 becomes movable, the reaction container unit 101 is moved to a substrate unloading place (not shown). If necessary, the substrate 505 is cooled to a desired temperature, and then an inert gas or the like is introduced into the reaction vessel 106 from a leak valve (not shown) to bring the inside of the reaction vessel 106 to atmospheric pressure. When the pressure inside the reaction vessel 106 becomes atmospheric pressure, the substrate 505 on which the deposited film is formed is taken out from the reaction vessel 106. Thereafter, when the reaction container 106 is again in a state where a deposited film can be formed by replacing or cleaning the components in the reaction container 106, the reaction container 106 is again subjected to the above-described substrate setting process.

In such a series of vacuum processing steps, it is efficient to prepare and use a plurality of reaction vessel parts 101. In this case, during the above-described series of steps, the reaction container unit 101 connected to the exhaust unit 102 completes the formation of the deposited film, and the reaction container unit 101 is separated from the exhaust unit 102. Is connected to the exhaust unit, and a deposited film is formed in the same manner.
The present invention has been described with reference to the electrophotographic photoreceptor forming apparatus and the forming method as an example. The reason for this is that the present invention has an effect of particularly preventing deposition film deposition. The present invention is not limited to this, and may be used in other vacuum processing steps such as etching and ion implantation, or other active gas such as sputtering and thermal CVD. Can be. Further, the present invention as described above is also effective when a plurality of vacuum processing steps are used and a part thereof is used.

The specific configuration of the connecting portion that can be used in the present invention is not particularly limited as long as the opening diameter on the reaction vessel side is different from the opening diameter on the exhaust means side. In addition to the configuration shown in FIG.
And a configuration as shown in FIG. The present invention is more effective when the opening diameter on the reaction vessel side is smaller than the opening diameter on the exhaust means side.

FIG. 4 is a schematic view of an example of a vacuum processing apparatus that can be used in the present invention. In FIG.
Denotes a movable reaction vessel part, a reaction vessel 603, a vacuum sealing valve 604 provided as needed, a connection flange 60.
2 and a carriage 609 on which the reaction vessel 603 is mounted and which can be moved. Reference numeral 605 denotes an exhaust unit, and an exhaust port is provided at a connection point of the movable reaction container unit 601.

FIG. 5A is a schematic diagram for more specifically explaining the connection point of the movable reaction vessel portion 601 to the exhaust portion 605 in FIG. The exhaust unit 605 is provided with an opening 608 having an opening diameter R integrally with the outer frame of the exhaust unit 605. A vacuum sealing material 606 for stopping is provided. Opening 608 of exhaust part 605
Is different from the opening diameter r of the opening 607 of the movable reaction vessel section 601. In FIGS. 4 and 5, the opening of the exhaust section 605 is made more effective so that the present invention is more effective. The opening diameter R of 608 is larger than the opening diameter r of the opening 607 of the movable reaction vessel part 601.

The vacuum processing apparatus of the present invention may be provided with one or more openings, for example, two openings. FIG. 5B is a schematic view of the exhaust unit 605 viewed from the opening 608 side. Two openings 608 provided integrally with the exhaust part 605 are provided in the lateral direction, and a vacuum seal member 606 is provided for each of the openings 608.
Is provided.

As described above, by providing the exhaust portion 605 with the two openings 608, the movable reaction container portion 60 is provided.
2 can be connected, and vacuum processing can be performed in parallel by these two movable reaction vessel portions 601. Even when such an apparatus shown in FIGS. 4 and 5 is used, the vacuum processing method is performed in the same manner as when the apparatus shown in FIGS. 1 and 2 is used. Thus, the exhaust unit 60
The number of movable reaction vessel portions 601 that can be connected to 5 may be plural, and the number is not particularly limited. It is appropriately determined in consideration of the gas flow rate used in the vacuum processing, the exhaust capacity of the exhaust unit, and the like. In the case where the exhaust unit 605 has a plurality of openings 608, it is not always necessary to connect the same number of movable reaction vessel units 601 as the number of the openings 608. For example, a configuration is adopted in which valves are installed between each opening 608 and the exhaust means, and after the required number of movable reaction vessel parts 601 are connected, only the valve corresponding to the connected opening 608 is opened. Vacuum processing can be performed in the same manner as in the case of the apparatus shown in FIGS.

In the present invention, the relationship between the opening diameter on the exhaust side and the opening diameter on the movable reaction vessel side is not particularly limited as described above, provided that they differ from each other. According to this, when the larger opening diameter is X and the smaller opening diameter is Y, the workability is extremely improved by setting Y / X ≦ 0.9. At this time, if each of the openings is machined with a machining dimensional accuracy of 1/10 mm scale, even if both are slightly overlapped, if the area is less than about 1% of the smaller opening area. For example, it can be said that the openings do not substantially overlap. In addition, the present invention becomes more effective by setting the opening diameter on the exhaust side to X and the opening diameter on the movable reaction container side to Y. In addition, the present invention provides an exhaust system that can seal a portion of the larger opening that does not overlap with the smaller opening with, for example, an annular rubber or the like, even if the opening area of the smaller opening is slightly reduced. The conductance does not substantially decrease and a high degree of vacuum can be maintained without being affected by the active gas. The outer diameter of the flange of the connecting portion may be appropriately determined in each device, but it is preferable that the outer diameter A of the movable container-side flange is A ≧ (2X−Y). Note that at least one of the opening of the reaction vessel and the opening of the exhaust unit may have a rectangular shape. In this case, the diagonal line of the rectangular shape is defined as the diameter. It is also preferable to provide a cooling means (not shown) on the member forming the opening provided on the reaction vessel side of the present invention.
By providing a cooling means (not shown), the active gas is cooled,
Since it can be prevented from reaching the member forming the opening provided on the exhaust means side, the degree of vacuum in the reaction vessel can be maintained at a high vacuum without impairing the adhesion between the reaction vessel and the exhaust means. I can do it. As another method for preventing the active gas from reaching the member forming the opening provided on the exhaust means side, for example, the member forming the opening provided on the reaction vessel side is lengthened, or a refrigerant is used. Cooling the member to collect ionic or neutral active species in the member, or provide a magnetic force means or an electric field generating means (not shown) outside the member to collect ionic active species. By doing so, the active species may be prevented from reaching the member forming the opening provided on the exhaust means. By using such an embodiment of the present invention, for example, an a-Si electrophotographic light receiving member as shown in FIG. 6 can be formed. FIG. 6 is a schematic configuration diagram for explaining a layer configuration of the a-Si-based electrophotographic light receiving member. An electrophotographic photosensitive member 700 shown in FIG.
Photoconductive layer 702 made of Si: H, X and having photoconductivity
Is provided. An electrophotographic photoreceptor 700 shown in FIG. 6B includes a photoconductive layer 702 made of a-Si: H, X and having photoconductivity and an amorphous silicon-based surface layer 703 on a support 701. It is configured. FIG.
The electrophotographic photoreceptor 700 shown in FIG.
A photoconductive layer 702 made of a-Si: H, X and having photoconductivity, and an amorphous silicon-based surface layer 703
And an amorphous silicon charge injection blocking layer 704. The photoconductor 700 for electrophotography shown in FIG. 6D has a photoconductive layer 702 provided on a support 701. The photoconductive layer 702 comprises a charge generation layer 705 and a charge transport layer 706 made of a-Si: H, X, on which an amorphous silicon-based surface layer 703 is provided.

The support for the photoreceptor may be conductive or electrically insulating. As the conductive support, Al,
Cr, Mo, Au, In, Nb, Te, V, Ti, P
Examples include metals such as t, Pd, and Fe, and alloys thereof, for example, stainless steel. Alternatively, phosphor bronze and the like can also be mentioned. 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 701 can be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface, and the thickness thereof is appropriately determined so as to form the electrophotographic photosensitive member 700 as desired. To be determined, electrophotographic photoreceptor 7
When flexibility as 00 is required, the support 70
The thickness can be reduced as much as possible within a range where the function as 1 can be sufficiently exhibited. However, the support 701 is usually 1 in terms of production, handling, mechanical strength and the like.
0 μm or more.

The photoconductive layer 702 is formed on the support 701 by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. In order to form the photoconductive layer 702, basically, Si capable of supplying silicon atoms (Si) can be used.
A source gas for supply, a source gas for H supply capable of supplying hydrogen atoms (H), and / or a source gas for X supply capable of supplying halogen atoms (X) in a reaction vessel capable of reducing the pressure inside To generate a glow discharge in the reaction vessel to form a layer of a-Si: H, X on a predetermined support 701 previously set at a predetermined position. .

It is necessary that the photoconductive layer 702 contains hydrogen atoms and / or halogen atoms.
This is because it is indispensable to compensate for the dangling bonds of silicon atoms and to improve the layer quality, particularly to improve the photoconductivity and the charge retention characteristics. Therefore, the content of the hydrogen atom or the halogen atom or the sum of the hydrogen atom and the halogen atom is preferably 10 to 40 atom%, more preferably 15 to 25 atom%, based on the sum of the silicon atom and the hydrogen atom and / or the halogen atom. It is desirable to be.

Substances that can serve as a Si supply gas include:
Silicon hydrides (silanes) in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or the like which can be gasified can be used effectively. SiH ₄ , Si ₂
H ₆ is mentioned as a preferable example. Then, hydrogen atoms are structurally introduced into the formed photoconductive layer 702 so that the introduction ratio of hydrogen atoms can be more easily controlled. In order to obtain good film characteristics, these gases are further added. H
It is also effective to mix a desired amount of a gas of silicon compound containing ₂ and / or He or a hydrogen atom to form a layer. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio. Examples of the effective source gas for supplying a halogen atom preferably include a gaseous or gasizable halogen compound such as a halogen gas, a halide, an interhalogen compound containing halogen, and a silane derivative substituted with halogen. 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 preferably used include fluorine gas (F ₂ ), BrF, ClF, C
Inter-halogen compounds such as IF ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned.

A silicon compound containing a halogen atom, so-called
Specific examples of the silane derivative substituted with a halogen atom include:
Typically, for example, SiF_Four, Si_TwoF₆Is preferred.
It can be mentioned as good. Photoconductive layer 702
Of hydrogen atoms and / or halogen atoms contained in
For example, the temperature of the support 701, the hydrogen atom
Or / and used to contain halogen atoms
Control the amount of raw materials introduced into the reaction vessel, discharge power, etc.
You have to control. Photoconductive layer 702 may be conductive as needed.
Is preferably contained. Conductivity
The atoms to be controlled are uniformly distributed in the photoconductive layer 702 without unevenness.
It may be contained in a cloth state, or in the layer thickness direction
May be present in a non-uniform distribution
No. The atoms that control the conductivity include semiconductors.
Can be mentioned, so-called impurities, p-type conduction
Atoms belonging to Group IIIb of the Periodic Table
IIIb atom) or provides n-type conduction properties
Atoms belonging to group Vb of the periodic table (hereinafter “Vb group atoms”
May be used. Group IIIb atom
Specifically, specifically, boron (B), aluminum (A
l), gallium (Ga), indium (In), tarium
(Tl), and B, Al, and Ga are particularly preferable.
You. Specific examples of group Vb atoms include phosphorus (P) and arsenic.
(As), antimony (Sb), bismuth (Bi), etc.
Yes, P and As are particularly preferred. Included in photoconductive layer 702
The content of atoms that control the conductivity
Or 1 × 10^-2~ 1 × 10^FourAtomic ppm, more preferred
Ku 5 × 10^-2~ 5 × 10^ThreeAtomic ppm, optimally 1 ×
10^-1~ 1 × 10^ThreePreferably, it is set to atomic ppm.
Atoms that control conductivity, for example, Group IIIb atoms or
In order to structurally introduce a group Vb atom,
The raw material for introducing a Group IIIb atom or a Group Vb source
Raw material for gas introduction into the reaction vessel in gaseous state
Introduced with other gases to form layer 702
Just do it. Raw material for introducing Group IIIb atoms or V
As a source material for introducing a group b atom,
It is gaseous at room temperature and pressure or at least under layer forming conditions.
It is desirable to employ one that can be easily gasified. That
As a raw material for introducing a group IIIb atom,
Is B for boron atom introduction._TwoH_Two, B_FourH_Ten, B_FiveH
₉, B_FiveH₁₁, B₆H_Ten, B₆H₁₂, B₆H₁₄Borohydride
Elementary, BF_Three, BCl_Three, BBr_ThreeSuch as boron halide
No. In addition, AlCl_Three, GaCl_Three, Ga (C
H_Three)_Three, InCl_Three, TlCl_ThreeAnd so on.
You. Effectively used as a raw material for introducing group Vb atoms
What is used for introducing phosphorus atoms is PH_Three, P_TwoH_FourEtc.
Phosphorus hydride, PH_FourI, PF_Three, PF_Five, PCl_Three, PC
l_Five, PBr_Three, PBr_Five, PI_ThreeAnd the like.
Can be In addition, AsH_Three, AsF_Three, AsCl_Three, As
Br_Three, AsF_Five, SbH_Three, SbF _Three, SbF_Five, SbC
l_Three, SbCl_Five, BiH_Three, BiCl_Three, BiBr_ThreeEtc.
Listed as effective starting materials for introducing group Vb atoms
Can be Also, the atoms that control these conductivity
The raw material for introduction may be changed to H_TwoAnd / or H
e may be used after dilution. Further, the photoconductive layer 70
3 is a carbon atom and / or an oxygen atom and / or a nitrogen atom
It is also effective to include a child. Carbon atoms and / or
Is the oxygen content and / or the nitrogen content is silicon
Atom, carbon atom, oxygen atom and nitrogen atom
Or 1 × 10^-Five-10 atomic%, more preferably 1 × 1
0^-Four~ 8 atomic%, optimally 1 × 10^-3~ 5 atomic% is desirable
New Carbon atom and / or oxygen atom and / or nitrogen
Atoms may be evenly and uniformly contained in the photoconductive layer
However, the unevenness such that the content changes in the thickness direction of the photoconductive layer.
There may be a part having a uniform distribution. Photoconductive layer 70
The layer thickness of 2 ensures that the desired electrophotographic properties are obtained and that the economy is low.
Is determined as desired from the point of
1 to 100 μm, more preferably 20 to 50 μm
m, optimally 23 to 45 μm. Place
To form the photoconductive layer 702 having desired film properties,
i. Mixing ratio of supply gas and dilution gas, gas in reaction vessel
Pressure, discharge power and substrate temperature as appropriate
is necessary. H used as dilution gas_TwoAnd / or
Or the flow rate of He has an optimal range as appropriate according to the layer design.
Selected. The gas pressure inside the reaction vessel was also designed in layers.
Therefore, the optimum range is appropriately selected.
× 10^-2~ 1.3 × 10^ThreePa, preferably 6.7 × 1
0^-2~ 6.7 × 10^TwoPa, optimally 1.3 × 10^-1~
1.3 × 10^TwoIt is preferably Pa. Shape photoconductive layer
The desired numerical range of the support temperature and gas pressure for
But the conditions are usually independent
Have desired properties, not determined separately
Based on mutual and organic relationships to form light-receiving members
It is desirable to determine the optimum value.

It is preferable to further form an amorphous silicon-based or amorphous carbon-based surface layer 703 on the photoconductive layer 702 formed on the support 701 as described above. The surface layer 703 is provided mainly for the purpose of improving moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability. The surface layer 703 can be made of any material as long as it is an amorphous silicon-based or amorphous carbon-based material.
For example, amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing a carbon atom (hereinafter referred to as “a-SiC: H, X”),
Amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing an oxygen atom (hereinafter referred to as “a-SiO: H, X”), a hydrogen atom (H) and / or a halogen Amorphous silicon containing an atom (X) and further containing a nitrogen atom (hereinafter referred to as “a-
SiN: H, X "), a hydrogen atom (H) and / or
Or amorphous silicon containing a halogen atom (X) and further containing at least one of a carbon atom, an oxygen atom, and a nitrogen atom (hereinafter referred to as “a-SiCON: H, X”); Materials such as amorphous carbon containing atoms (H) and / or halogen atoms (X) (hereinafter referred to as “aC: H, X”) are preferably used. The surface layer 703 is formed by a vacuum deposition film formation method with appropriately setting film forming parameter numerical conditions so as to obtain desired characteristics. For example, a-Si
In order to form the surface layer 703 composed of C: H, X, a source gas for supplying Si that can supply silicon atoms (Si) and a gas for supplying C that can supply carbon atoms (C) are basically used. A raw material gas and a raw material gas for supplying H that can supply hydrogen atoms (H) or / and a raw material gas for X supply that can supply halogen atoms (X) are placed in a reaction vessel capable of reducing the pressure inside a desired reaction vessel. Introduced in a gaseous state, a glow discharge is generated in the reaction vessel, and a-SiC: H, X is formed on a support 701 on which a photoconductive layer 702 previously set at a predetermined position is formed.
May be formed. Further, it is necessary that the surface layer 603 contains hydrogen atoms and / or halogen atoms, which compensates for the dangling bonds of silicon atoms and improves the layer quality, in particular, photoconductive properties and charge retention. It is important to improve the characteristics. In general, the hydrogen content is desirably 30 to 70 atomic%, preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic%, based on the total amount of the constituent atoms. The content of fluorine atoms is usually 0.01 to 15 atomic%, preferably 0.1 to 10 atomic%.
Atomic%, optimally 0.6 to 4 atomic% is desirable.

Silicon used in forming the surface layer
(Si) Substances that can be supply gas include Si
H_Four, Si_TwoH₆, Si_ThreeH₈, Si_FourH_TenEtc. in the gas state,
Alternatively, silicon hydrides (silanes) that can be gasified
To be used, and handling when creating layers
SiH in terms of easiness and good Si supply efficiency_Four, Si_TwoH₆
Are preferred. In addition, these Si
If necessary, supply the source gas for H_Two, He, Ar, N
It may be used after being diluted with a gas such as e. For carbon supply
As a substance that can be a gas, CH_Four, C_TwoH₆, C
_ThreeH₈, C_FourH_TenGaseous or gasifiable charcoal such as
Hydrogen hydride is mentioned as being used effectively.
In terms of ease of handling during preparation and good Si supply efficiency, C
H_Four, C_TwoH₆Are preferred. Also,
If necessary, the raw material gas for supplying C may be replaced with H if necessary._Two, H
e, Ar, Ne, etc.
No. As a substance that can be a gas for supplying nitrogen or oxygen
Is NH_Three, NO, N_TwoO, NO _Two, O_Two, CO, CO_Two,
N_TwoEffective in gaseous or gaseous compounds such as
To be used. Also, these
The raw material gas for supplying oxygen and oxygen_Two, He,
It may be used after being diluted with a gas such as Ar or Ne. Ma
Of hydrogen atoms introduced into the surface layer 703 to be formed.
To make it easier to control the introduction ratio
And these gases further contain hydrogen gas or hydrogen atoms
It is preferable to form a layer by mixing a desired amount of a silicon compound gas.
Good. In addition, each gas is not limited to a single species,
May be mixed. halogen
For example, halo is useful as a source gas for supplying atoms.
Gen gas, halide, halogen including halogen
Gaseous compounds, halogen-substituted silane derivatives, etc.
Or halogenated compounds which can be gasified are preferred.
It is. In addition, silicon atoms and halogen atoms
Gaseous or gasifiable halogen constituents
Silicon hydride compounds containing atoms are also listed as effective
be able to. Halogen that can be suitably used in the present invention
As the compound, specifically, fluorine gas (F_Two), Br
F, ClF, ClF_Three, BrF3, BrF_Five, IF_Three, I
F₇And the like. Halo
A silicon compound containing a gen atom, a so-called halogen atom
Specific examples of the substituted silane derivative include, for example,
SiF_Four, Si_TwoF₆Etc. are preferred.
Can be mentioned.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer 703, for example, the temperature of the support 701, a raw material used to contain hydrogen atoms and / or halogen atoms The discharge power and the like to be introduced into the reaction vessel may be controlled.

The carbon atoms and / or oxygen atoms and / or nitrogen atoms may be uniformly contained in the surface layer, or may be non-uniform such that the content changes in the thickness direction of the surface layer. There may be a portion having a distribution. Further, it is preferable that the surface layer 703 contain atoms for controlling conductivity as necessary. The atoms for controlling the conductivity may be contained in the surface layer 703 in a state of being uniformly distributed in the surface layer 703, or even if there is a part contained in the layer thickness direction in a non-uniform distribution state. Good.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors, and atoms belonging to Group IIIb of the Periodic Table giving p-type conduction characteristics (hereinafter referred to as “Group IIIb atoms”). (Abbreviated) or an atom belonging to Group Vb of the periodic table that provides n-type conduction characteristics (hereinafter abbreviated as “Vb group atom”).

Specific examples of Group IIIb atoms include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). It is suitable. Group Vb atoms include:
Specifically, phosphorus (P), arsenic (As), antimony (S
b), bismuth (Bi) and the like, and P and As are particularly preferable.

The content of atoms for controlling conductivity contained in the surface layer 703 is preferably 1 × 10 ⁻³ to 1 ×.
10 ³ atomic ppm, more preferably 1 × 10 ^{-2 to} 5 × 1
0 ² atomic ppm, optimally 1 × 10 ^-1 to 1 × 10 ² atomic p
pm. In order to structurally introduce an atom for controlling conductivity, for example, a group IIIb atom or a group Vb atom, a source material for introducing a group IIIb atom or a group material for introducing a group Vb atom may be used in forming a layer. The raw material may be introduced in a gaseous state into the reaction vessel together with another gas for forming the surface layer 703.

As a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom,
It is desirable to employ one that is gaseous at normal temperature and normal pressure or that can be easily gasified at least under layer forming conditions. Specific examples of such a raw material for introducing a group IIIb atom include B ₂ H ₆ , B ₄ H ₁₀ , and B ₅ H for introducing a boron atom.
_{9, B 5 H 11, B} 6 H 10, B 6 H 12, B 6 H 14 borohydride such as, BF _3, BCl _3, BBr boron halides such as _3.

In addition, AlCl_Three, GaCl_Three, Ga (C
H_Three)_Three, InCl_Three, TlCl_ThreeAnd so on.
You. Effectively used as a raw material for introducing group Vb atoms
The reason for this is that PH is introduced for introducing phosphorus atoms._Three, P_TwoH_Fouretc
Phosphorus hydride, PH_FourI, PF_Three, PF_Five, PCl_Three, PCl
_Five, PBr_Three, PBr_Five, PI_ThreeAnd halogenated phosphorus such as
It is. In addition, AsH _Three, AsF_Three, AsCl_Three, AsB
r_Three, AsF_Five, SbH_Three, SbF_Three, SbF_Five, SbC
l_Three, SbCl_Five, BiH_Three, BiCl_Three, BiBr_ThreeEtc.
Listed as effective starting materials for introducing group Vb atoms
Can be Also, the atoms that control these conductivity
The raw material for introduction may be changed to H_Two, He, Ar, N
It may be used after being diluted with a gas such as e. Surface layer 70
The layer thickness of 3 is usually 0.01 to 3 μm, preferably
0.05-2 μm, optimally 0.1-1 μm
Is desirable. Layer thickness less than 0.01 μm
Surface layer is lost due to abrasion etc.
If it exceeds 3 μm, the electric potential such as an increase in the residual potential will increase.
Deterioration of the photographic characteristics is observed. The surface layer 703 is
Carefully shape it to give the desired properties as desired
Is done. That is, Si, C and / or N and / or
Substances containing O, H and / or X as their constituents form
Depending on the conditions, it can be structurally from crystalline to amorphous
State, electrical properties from conductive to semiconductive, insulating
Properties from photoconductive to non-photoconductive
In the present invention, each of the properties up to the quality is shown.
A compound having desired properties according to the purpose is formed
The choice of the forming conditions is strictly made as desired.
You. For example, the main purpose of the surface layer 703 is to improve the pressure resistance.
In order to provide electrical insulation,
Created as a prominent non-single crystal material. Also, continuous repetition
The main purpose is to improve the use characteristics and the use environment characteristics.
When the surface layer 703 is provided,
The degree is relaxed to some extent, and it is
It is formed as a non-single crystal material having a high sensitivity. Purpose
To form a surface layer 703 having characteristics capable of achieving
Sets the temperature of the support 701 and the gas pressure in the reaction vessel to a desired value.
Therefore, it is necessary to set appropriately. Of the support 701
The optimum range of the temperature (Ts) is appropriately selected according to the layer design.
In general, preferably 200 to 350
° C, more preferably 230-330 ° C, optimally 250
It is desirable to set it to 300 ° C. The gas pressure inside the reaction vessel
Similarly, the optimum range is appropriately selected according to the layer design.
Normally, preferably 1.3 × 10^-2~ 1.3 × 10
^ThreePa, more preferably 6.7 × 10^-2~ 6.7 × 10^Two
Pa, optimally 1.3 × 10^-1~ 1.3 × 10^TwoPa and
Is preferred. Support temperature to form surface layer
The above ranges are listed as desirable numerical ranges of the pressure and the gas pressure.
Conditions are usually determined independently and separately
Rather than forming a light receiving member with the desired properties.
Determine optimal values based on mutual and organic relationships
Is desirable. Further, between the surface layer 703 and the photoconductive layer 702
Carbon atom and / or oxygen atom and / or nitrogen atom
Decreases continuously toward the photoconductive layer 702
A region may be provided. This makes the surface layer and the photoconductive layer denser.
Improves adhesion and reduces the effects of interference due to light reflection at the interface
And at the same time carry at the interface.
(I) trapping of the photoconductor is prevented, and the photoconductor characteristics can be improved.

If necessary, the conductive support and the photoconductive layer
In the meantime, it works to prevent charge injection from the conductive support side
A charge injection blocking layer 704 having a layer may be provided. Sand
That is, the charge injection blocking layer 604 is used to charge the photoreceptor with a constant polarity
When the surface is treated, the electric charge is applied from the support side to the photoconductive layer side.
It has a function to prevent the load from being injected, and a band of the opposite polarity
Such functions are not exhibited when subjected to electric treatment,
It has a so-called polarity dependency. With such a function
The charge injection blocking layer 704 has conductivity control to provide
Relatively more atoms than the photoconductive layer. The layer
The atoms that control the conductivity contained in the
Or evenly distributed in the thickness direction.
Although it is contained evenly, it is contained in a state of non-uniform distribution.
There may be a part to have. When the distribution concentration is not uniform
In such a case, it is necessary to include it so that it is more distributed on the support side.
It is suitable. However, in each case the support
In a direction parallel to the surface and in a plane parallel to the surface
To ensure uniform properties in the in-plane direction
It is necessary from the point of view. Contained in the charge injection blocking layer 704
In the field of semiconductors, atoms that control conductivity
P-type conduction characteristics
An atom belonging to Group IIIb of the Periodic Table (hereinafter referred to as “IIIb
Group), or a period giving n-type conduction properties
An atom belonging to the group Vb of the table (hereinafter abbreviated as “group Vb atom”)
Described below) can be used. Group IIIb atom
Specifically, B (boron), Al (aluminum)
), Ga (gallium), In (indium), Tl
(Thallium) and the like, and B, Al, and Ga are particularly preferable.
You. Specific examples of group Vb atoms include P (phosphorus) and A
s (arsenic), Sb (antimony), Bi (bismuth), etc.
And P and As are particularly preferable. Charge injection blocking layer 7
04 as the content of atoms controlling conductivity contained in
Is determined as desired, but is preferably
10-1 × 10^FourAtomic ppm, more preferably 50-5 ×
10^ThreeAtomic ppm, optimally 1 × 10^Two~ 1 × 10^Threeatom
It is desirably set to ppm. Furthermore, a charge injection blocking layer
704 contains less carbon, nitrogen and oxygen atoms.
The charge injection blocking layer
Adhesion with other layers provided in direct contact with 704
Can be further improved. Contained in the layer
Carbon or nitrogen or oxygen atoms in the layer
It may be evenly distributed evenly or in the thickness direction
Are distributed uniformly, but are distributed unevenly
There may be a part contained in the state. However,
In each case, in a direction parallel to the surface of the support
Can be uniformly distributed and evenly distributed in the in-plane direction.
This is also necessary from the viewpoint of making the characteristics uniform. charge
Carbon atoms contained in the entire region of the injection blocking layer 704;
Content of nitrogen atoms and / or oxygen atoms is
Appropriately determined so that the object of the present invention is effectively achieved.
However, in the case of one kind, the amount is used.
Is preferably 1 × 10^-3~ 50 at.%
More preferably 5 × 10^-3~ 30 atomic%, optimally 1 × 10
^-2Desirably, it is set to 10 to 10 atomic%. Also charge injection
Hydrogen atoms and / or halo contained in the blocking layer 704
Gen atoms compensate for dangling bonds present in the layer and improve film quality
Is effective. Hydrogen atoms in the charge injection blocking layer 704
Or a halogen atom or the sum of a hydrogen atom and a halogen atom
Is preferably 1 to 50 atomic%, more preferably 5 atomic%.
~ 40 atomic%, optimally 10-30 atomic%
Good. The thickness of the charge injection blocking layer 704 is the desired
It is preferable from the viewpoint of obtaining characteristics and economic effects.
0.1 to 5 μm, more preferably 0.3 to 4 μm,
Most preferably, it is 0.5 to 3 μm. Charge note
To form the blocking layer 704, the above-described photoconductive layer is formed.
A vacuum deposition method similar to the above method is employed. Photoconductive layer 7
Mixing of Si supply gas and diluent gas as in 02
Ratio, gas pressure in the reaction vessel, discharge power and support 70
It is necessary to appropriately set the temperature of No. 1. With dilution gas
Some H _TwoAnd / or He flow rate depends on the layer design,
Therefore, the optimum range is selected as appropriate,
H_TwoAnd / or He is usually 1 to 20 times,
Preferably, the range is 3 to 15 times, and most preferably, 5 to 10 times.
It is desirable to control. The gas pressure in the reaction vessel is also
The optimal range is selected as appropriate according to the design,
1.3 × 10^-2~ 1.3 × 10^ThreePa, preferably
6.7 × 10^-2~ 6.7 × 10^TwoPa, optimally 1.3
× 10^-1~ 1.3 × 10^TwoIt is preferably Pa. Electric
Mixing of diluent gas to form the load blocking layer 704
Desirable numerical ranges of ratio, gas pressure, discharge power and support temperature
The ranges described above can be cited as examples.
Actors are usually not independently determined separately.
To form a charge injection blocking layer having desired characteristics.
Of each layer formation factor based on mutual and organic relevance
It is desirable to determine the optimal value. Support 701 and photoconductive layer
702 or the charge injection blocking layer 704
For the purpose of further improvement, for example, Si_ThreeN_Four, Si
O_Two, SiO, or silicon atoms as the base and hydrogen
Atom and / or halogen atom and carbon atom and / or
Is an amorphous material containing oxygen atoms and / or nitrogen atoms, etc.
May be provided. In addition, from the support
Absorption to prevent interference patterns from occurring due to reflected light
A layer may be provided.

[0049]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto. (Example 1) Using the vacuum processing apparatus shown in FIGS. 1 and 2,
Using the reaction container for forming an electrophotographic photosensitive member shown in FIG. 3 as the reaction container 106, the diameter is 80 mm and the length is 358 mm.
An a-Si photosensitive member was formed on the cylindrical aluminum cylinder 505 under the conditions shown in Table 1 with the oscillation frequency of the high-frequency power supplies 503 and 514 set to 100 MHz. In Table 1, the power indicates the total value of each power supplied from the high frequency power supply 503 and the high frequency power supply 514. The opening diameter r of the connection part on the reaction vessel side was 24 cm, and the opening diameter R of the connection part on the exhaust part side was 30 cm. The flange outer diameter A of the reaction vessel side connection part and the exhaust part side connection part were both 40 cm.
The cathode electrodes 502 and 506 are made of SUS having a diameter of 20 mm.
It is a cylinder made of 21 mm inside diameter and 24 mm outside diameter
The structure was covered with an alumina pipe. The alumina pipe was blasted to have a surface roughness of 20 μm in Rz with a reference length of 2.5 mm. The raw material gas supply means 512 has an alumina pipe having an inner diameter of 10 mm and an outer diameter of 13 mm, and has a structure in which an end is sealed, and a raw material gas can be supplied from a 1.2 mm diameter gas jet port provided on the pipe. Was used. The surface of the raw material gas supply means 512 was blasted to have a surface roughness of 20 μm in Rz with a reference length of 2.5 mm. Formation of a deposited film using such an apparatus was roughly as follows. First, the movable reaction vessel unit 101 was connected to a substrate installation exhaust device (not shown) by a connection flange 104, and at the same time, an Ar supply pipe (not shown) and a power supply line to the reaction vessel unit 101 were also connected. In the state, the cylindrical substrate 505 is
1 (106). Subsequently, the vacuum sealing valve 108
Was opened, and the inside of the reaction vessel 501 was evacuated through the exhaust pipe 511 by the exhaust device for substrate installation. Reaction vessel 501 (10
6) After confirming that the inside was evacuated to 1 × 10 ⁻³ Pa or less, 500 sccm of Ar was supplied from the raw material gas supply means 512 into the reaction vessel 501 (106), and the reaction was performed by a pressure adjustment valve (not shown). The cylindrical body 505 is heated to 250 ° C. by the heating element 507 while maintaining the pressure in the container at 70 Pa.
And controlled for 2 hours. During this time,
The cylindrical substrate 505 was rotated at a speed of 10 rpm by a motor 509 via a rotating shaft 508 and a gear 510. Next, the vacuum sealing valve 108 is closed, and the reaction vessel 501 (10
6) When the internal pressure reached 200 Pa, the supply of Ar was stopped, and the heating of the base 505 by the heating element 507 was stopped. After that, the connection flange 104 was cut off from the exhaust device for installing the substrate, and at the same time, the Ar supply pipe (not shown) connected to the raw material gas supply means 512 and the power supply line to the reaction vessel 101 were also cut off. Subsequently, the movable reaction vessel section 101 is moved to the place where the exhaust section 102 is installed, and the connection flange 104 is connected to the exhaust section side connection flange 1.
05 was connected via an O-ring (vacuum seal material) 110 made by Viton, and the connection portion 103 was fixed by a clamp. A source gas supply pipe (not shown) is connected to source gas supply means 512, and
1 and a high-frequency power supply cable were connected. After these connections are completed, first, the evacuation unit side vacuum sealing valve 109 is opened, the inside of the pipe is evacuated by the evacuation means 107, and then the reaction container side vacuum sealing valve 108 is opened, and the inside of the reaction vessel 106 is 1 × 10 ^The air was evacuated to ^-3 Pa or less. Then, while rotating the cylindrical base 505 at a speed of 10 rpm by the motor 509 via the rotating shaft 508 and the gear 510, 500 sccm of Ar is supplied from the raw material gas supply means 512 into the reaction vessel 501 to adjust the pressure (not shown). The cylindrical substrate 505 was again heated and controlled at 250 ° C. by the heating element 507 while maintaining the pressure inside the reaction vessel at 70 Pa by the valve, and this state was maintained for 20 minutes. Then A
The supply of r is stopped, and via the raw material gas supply means 512,
Source gases used for forming the charge injection blocking layer shown in Table 2 were introduced. After confirming that the flow rate of the raw material gas has reached the set flow rate and that the pressure in the reaction vessel 501 (106) has stabilized, the output values of the high-frequency power supplies 503 and 514 are set to the powers shown in Table 1, and the matching box is set. High-frequency power was supplied to the cathode electrodes 502 and 506 via 504 and 513. From the cathode electrodes 502 and 506, the reaction vessel 501
The charge injection blocking layer was formed on the cylindrical substrate 505 by exciting and dissociating the source gas with the high-frequency power radiated into (106). After the formation of the predetermined film thickness, the supply of the high-frequency power was stopped, the supply of the source gas was stopped, and the formation of the charge injection blocking layer was completed. By repeating the same operation a plurality of times, a photoconductive layer and a surface layer were sequentially formed. After the deposition film forming step is completed in this manner, the source gas in the reaction vessel 501 (106) and the source gas supply pipe is sufficiently purged.
08 and 109 were closed. In this state, the reaction vessel 501 (1
06) is introduced into the connection portion 10 after introducing He at 1000 Pa.
3 and at the same time, the raw material gas supply pipe, the power supply line, and the high-frequency power supply cable were disconnected, and the reaction vessel 101 was made movable. Next, the reaction vessel section 1
01 to the substrate unloading place, and after cooling the substrate 505 to room temperature, a reaction valve 501 (1
06), nitrogen was introduced into the reaction vessel 501 (106) to atmospheric pressure. When the inside of the reaction vessel 501 (106) became atmospheric pressure, the substrate 505 on which the deposited film was formed was taken out from the inside of the reaction vessel 501 (106). After that, when the components in the reaction vessel 501 (106) were replaced to put the reaction vessel 501 (106) in a state in which a deposited film could be formed again, a series of a-Si photoconductor forming steps were completed. In this way, 20 lots of a-Si-based photoconductors were formed under the conditions shown in Table 1. As a result, the movable reaction vessel section 1
It was confirmed that attachment / detachment to / from the exhaust unit 102 could be performed extremely easily, and the work efficiency was also high.

(Comparative Example 1) As in Example 1, using the vacuum processing apparatus shown in FIGS. 1 and 2 used in Example 1 and the reaction vessel for forming an electrophotographic photosensitive member shown in FIG. Thus, 20 lots of the a-Si type photoreceptor were formed. However, both the opening diameter r of the reaction vessel side connection part and the opening diameter R of the exhaust part side connection part in FIGS. 1 and 2 were 24 cm. The flange outer diameter A of the reaction vessel side connection part and the exhaust part side connection part was both kept at 40 cm. As a result, the movable reaction vessel section 1
It was found that positioning of the attachment / detachment to / from the exhaust unit 102 was difficult, and workability was poor as compared with the first embodiment. In addition, even if five times as long as the connection work time in the first embodiment has elapsed, if accurate positioning has not been performed, the positioning is terminated at that point, and the state is determined in which accurate positioning is not performed. After connecting the movable reaction vessel section 101 to the exhaust section 102 and confirming that the connection section was properly vacuum-sealed, the process was advanced to the next step. By such a connection work, 2
Accurate positioning was not performed for 4 lots out of 0 lots. Thus, the a-S fabricated in Example 1 and Comparative Example 1
The i-type photoconductor was installed in a Canon copier NP-6750 modified for this test, and the "characteristic variation" of the photoconductor was set.
Was evaluated. The specific evaluation method of “variation in characteristics” was as follows. Characteristic variation In the following three items, the maximum value / minimum value of the evaluation results of all photoconductors in each evaluation is obtained, and then (maximum value) /
(Minimum value) was determined. Of the four items, the one with the largest value was taken as the value of the characteristic variation. Therefore, the smaller the numerical value, the better. Charging ability Measures the dark area potential at the developing device when a constant current is applied to the main charger of the copying machine. Therefore, the higher the dark area potential, the better the charging ability. The charging ability was measured over the entire area of the photoconductor in the generatrix direction, and evaluated based on the lowest potential in the dark area. Sensitivity After adjusting the main charger current so that the dark area potential at the developing device position becomes a constant value, use a predetermined white paper with a reflection density of 0.01 or less for the original, and set the bright area potential at the developing device position to a predetermined value. The evaluation is made based on the image exposure light amount when the image exposure light amount is adjusted so as to be as follows. Therefore, the smaller the image exposure light amount, the better the sensitivity. The sensitivity was measured over the entire area of the photoconductor in the generatrix direction, and evaluated based on the maximum image exposure light amount in the area. After adjusting the current value of the main charger so that the dark portion potential at the developing device position becomes a predetermined value, the image exposure light amount is adjusted so that the light portion potential when a predetermined white paper is used as a document becomes a predetermined value. adjust. In this state, a ghost test chart (part number: FY9-9040) manufactured by Canon Inc. has a reflection density of 1.1 and a diameter of 5
The reflection density of the black circle with a diameter of 5 mm of the ghost chart recognized on the halftone copy in a copy image obtained by placing a black circle of mm on a platen and overlaying a halftone chart made by Canon on the platen The measurement was performed by measuring the difference between the reflection density of the halftone part and the reflection density of the halftone part. The optical memory measurement was performed over the entire area of the photoconductor in the generatrix direction, and the evaluation was made based on the maximum reflection density difference therein. As a result of the evaluation, the “characteristic variation” of the photoconductor manufactured in Example 1 was 15% smaller than the “characteristic variation” of the photoconductor manufactured in Comparative Example 1, and the “characteristic variation” was small according to the present invention. Good a-
It has also been found that a Si-based photoreceptor can be formed.
Further, the electrophotographic image formed by using the electrophotographic photoreceptor produced in Example 1 was very good without any image deletion or the like.

[0051]

[Table 1] (Embodiment 2) Using the vacuum processing apparatus shown in FIGS. 4 and 5,
As the reaction vessel 603, the reaction vessel for forming an electrophotographic photosensitive member shown in FIG. 7 was used, and the diameter was 80 mm and the length was 358 mm.
An a-Si photoreceptor was formed on the cylindrical aluminum cylinder 2112 of No. 1 under the conditions shown in Table 2 with the oscillation frequency of a high frequency power supply (not shown) set to 50 MHz. The basic structure of the reaction container for forming an electrophotographic photoreceptor shown in FIG. 7 is the same as that of the reaction container for forming an electrophotographic photoreceptor shown in FIG. 9, but the exhaust pipe 801 is shown in FIG. 4 and FIG. It has been modified so that it can be connected to a vacuum processing device. The opening diameter r of the reaction vessel side connection part was 10 cm, and the opening diameter R of the exhaust part side connection part was 12 cm. In addition, the reaction vessel connection flange 60
The outer diameter of 2 was 18 cm. The formation of a deposited film using such an apparatus is performed by using two movable reaction vessel parts 60 in the exhaust part 605.
The procedure was performed in substantially the same manner as in Example 1 except that No. 1 was connected.
As a result, it was confirmed that attachment and detachment of the movable reaction vessel section 601 to and from the exhaust section 605 could be performed extremely easily, and the working efficiency was high.

(Comparative Example 2) As in Example 2, using the vacuum processing apparatus shown in FIGS. 4 and 5 used in Example 2 and the reaction vessel for forming an electrophotographic photosensitive member shown in FIG. Thus, 20 lots of the a-Si type photoreceptor were formed. 4 and 5, the opening diameter r of the reaction vessel side connection part and the opening diameter R of the exhaust part connection part were both 10 cm, and the outer diameter of the reaction vessel connection flange 602 was kept at 18 cm. As a result, it was difficult to position the movable reaction container section 601 to and from the exhaust section 605, and the workability was poor as compared with the second embodiment. In addition, even if five times the connection work time in the second embodiment has elapsed, if accurate positioning has not been performed, the positioning is terminated at that time, and the state is determined in which accurate positioning is not performed. After connecting the movable reaction vessel section 601 to the exhaust section 605 and confirming that the vacuum sealing of the connection section has been normally performed, the process proceeds to the next step. Due to such connection work, accurate positioning was not performed for two lots out of 20 lots. Thus, the a-Si photoconductors manufactured in Example 2 and Comparative Example 2 were installed in a Canon copier NP-6750 modified for this test, and evaluation was made on “characteristic variation” of the photoconductors. Done. The specific evaluation method of “variation in characteristics” was the same as in Example 1. As a result of the evaluation, “variation in characteristics” of the photoreceptor manufactured in Example 2
Is 11% smaller than the “characteristic variation” of the photoconductor manufactured in Comparative Example 2, and it is also clear that a good a-Si-based photoconductor with small “characteristic variation” can be formed by the present invention. Was. Further, the electrophotographic image formed using the electrophotographic photoreceptor produced in Example 2 was very good without any image deletion or the like.

[0053]

[Table 2] (Embodiment 3) The vacuum processing apparatus shown in FIGS. 4 and 5, FIG.
Was used to clean the adhered film in the reaction vessel. The frequency of the high frequency power used for cleaning was 13.56 MHz. First, a photosensitive member was formed using the vacuum processing apparatus and the reaction vessel used in Example 2 in the same manner as in Example 2, and the substrate 2112 on which the deposited film was formed was taken out from the reaction vessel 603 (2101). Subsequently, after a cleaning base is installed in the reaction vessel 603 (2101), the movable reaction vessel section 601 is moved to a cleaning stage provided with the cleaning exhaust section 605 having the configuration shown in FIGS. Connected to this.
The specific connection procedure was the same as in the first and second embodiments. After the connection is completed, the vacuum sealing valve 604 is opened and the reaction vessel 60 is opened.
3 (2101) was evacuated to 1 × 10 ⁻³ Pa or less.
Thereafter, the raw material gas for cleaning shown in Table 3 was introduced through the raw material gas introduction pipe 2114. The flow rate of the source gas becomes the set flow rate, and the reaction vessel 603 (2101)
After confirming that the internal pressure was stabilized, the output value of the high frequency power supply (not shown) was set to the power shown in Table 3, and high frequency power was supplied to the cathode electrode 2111 via the matching box 2115. The source gas is excited and dissociated by the high-frequency power radiated into the reaction vessel 603 (2101) from the cathode electrode 2111 to generate active species, and the active species forms a deposited film adhered in the reaction vessel 603 (2101). Cleaned. Reaction vessel 603
After the adhered film in (2101) was completely removed, the source gas in the reaction vessel 603 (2101) and the source gas introduction pipe was sufficiently purged, and then the vacuum sealing valve 604 was closed. In this state, the movable reaction vessel section 601 was separated from the cleaning exhaust section 605 in the same procedure as in Examples 1 and 2. Next, the cleaning substrate was taken out of the reaction container 603 (2101), and the process again proceeded to the photoconductor forming step. The opening diameter r of the movable reaction vessel part 601 is 10 cm, which is the same as that of the second embodiment.
The opening diameter R of No. 5 was 8 cm. The outer diameter of the reaction vessel connection flange 602 is 18 cm, which is the same as in the second embodiment. Such a cleaning step was performed 20 times under the conditions shown in Table 3. As a result, the exhaust section 605 of the movable reaction vessel section 601
It was confirmed that attachment to and detachment from the device could be performed very easily, and work efficiency was high. Further, the reaction vessel 603 (21
01) It was confirmed that the cleaning of the adhered film in No. 01) was performed well without any problem. Furthermore, the electrophotographic photoreceptor formed by a series of photoreceptor forming steps including such a cleaning step had no problem in characteristics, and the electrophotographic image formed by using the electrophotographic photoreceptor was extremely good. .

(Comparative Example 3) Using the vacuum processing apparatus and the reaction container used in Example 3, the adhered film in the reaction container was cleaned 20 times in the same manner as in Example 3. However, the opening diameter R of the cleaning exhaust unit 605 was set to 10 cm, which is the same as the opening diameter r of the movable reaction container unit 601. As a result, it was found that positioning of the movable reaction vessel unit 601 to and from the cleaning exhaust unit 605 was difficult, and workability was poor compared to the third embodiment. Also, even if five times as long as the connection work time in the third embodiment has elapsed, if accurate positioning has not been performed, the positioning is terminated at that point, and the state is determined in which accurate positioning is not performed. The movable reaction container 601 was connected to the cleaning exhaust unit 605, and after confirming that the connection was vacuum-sealed normally, the process was advanced to the next step. By such a connection work, 3 out of 20 times
The times were not accurately positioned. In addition, the time required for cleaning the adhered film in the reaction vessel 603 (2101) was not constant and varied. The electrophotographic photoreceptor formed by a series of photoreceptor forming steps including such a cleaning step had no problem in characteristics, and an electrophotographic image formed by using the same was satisfactory.

[0055]

[Table 3] (Embodiment 4) Using the vacuum processing apparatus shown in FIGS. 1 and 2,
As the reaction vessel 106, the reaction vessel for forming an electrophotographic photoreceptor shown in FIG.
On the cylindrical aluminum cylinder 905, 20 lots of a-Si photosensitive members were formed under the conditions shown in Table 4 with the oscillation frequency of the high frequency power supply 903 set to 450 MHz. 8A is a schematic cross-sectional view, and FIG.
It is a schematic sectional drawing which follows the cutting line AA 'of (a). An exhaust pipe 911 is formed on the side surface of the reaction vessel 901, and the other end of the exhaust pipe 911 is connected to the vacuum sealing valve 10 in FIGS. 1 and 2.
8 is connected. The opening of the exhaust pipe is provided with a conductive mesh (not shown) in order to prevent high-frequency power introduced into the reaction vessel from leaking to the exhaust means side. The cylindrical substrate 905 on which the deposited film is formed is disposed at the center of the reaction vessel 901. The base 905 is held by a rotating shaft 908, and when the motor 909 is driven, the reduction gear 91
The rotation axis 908 rotates through the axis 0, and the cylindrical base 905 rotates around its central axis in the generatrix. Further, the cylindrical base 905 can be heated by the heating element 907. The high-frequency power output from the high-frequency power supply 903 is supplied from the cathode electrode 902 into the reaction vessel 901 which is a film formation space via the matching box 904 and the high-frequency power supply cable 915. Source gas supply means 912 is provided in the reaction vessel 901 to supply a desired source gas into the reaction vessel 901. The opening diameter r of the reaction vessel side connection part was 15 cm, and the opening diameter R of the exhaust part side connection part was 21 cm. In addition, the reaction vessel connection flange 6
02 had an outer diameter of 30 cm. Formation of a deposited film using such an apparatus was performed in the same manner as in Example 1. As a result, it was confirmed that attachment and detachment of the movable reaction vessel section 601 to and from the exhaust section 605 could be performed extremely easily, and the working efficiency was high.

(Comparative Example 4) The same as Example 4 except that the vacuum processing apparatus shown in FIGS. 1 and 2 used in Example 4 and the electrophotographic photosensitive member forming reaction vessel shown in FIG. 8 were used. Thus, 20 lots of the a-Si type photoreceptor were formed. However, the opening diameter r of the connection part on the reaction vessel side and the opening diameter R of the connection part on the exhaust part side in both FIGS. 1 and 2 were 15 cm. The flange outer diameter A of the reaction vessel side connection part and the exhaust part side connection part was both kept at 30 cm. As a result, the movable reaction vessel section 10
It was found that positioning of the attachment / detachment to / from the exhaust portion 102 was difficult, and workability was poor as compared with the fourth embodiment. Also, even if five times as long as the connection work time in the fourth embodiment has elapsed, if accurate positioning has not been performed, the positioning is terminated at that point in time, and accurate positioning is not performed. After connecting the movable reaction vessel section 101 to the exhaust section 102 and confirming that the connection section was properly vacuum-sealed, the process was advanced to the next step. By such connection work, 20
Accurate positioning was not performed for three of the lots.
As described above, the a-Si type photoreceptor produced in Example 4 and Comparative Example 4 was modified for this test by Canon copier N.
The photoconductor was set on a P-6030 and evaluated for "characteristic variation" of the photoconductor. The specific evaluation method of “variation in characteristics” was the same as in Example 1. As a result of the evaluation, the “characteristic variation” of the photoconductor manufactured in Example 4 was 13% smaller than the “characteristic variation” of the photoconductor manufactured in Comparative Example 4.
Good a-Si with small "characteristic variation" according to the present invention
It was also clarified that a system photoreceptor could be formed. Further, the electrophotographic image formed using the electrophotographic photoreceptor produced in Example 4 was an extremely good one having no image deletion or the like.

[0057]

[Table 4]

[0058]

As described above, according to the present invention, a reaction vessel which can be depressurized and an exhaust means for exhausting gas introduced into the reaction vessel are provided. In a vacuum processing apparatus that can be attached to and detached from the evacuation unit, the attachment and detachment of the reaction container can be performed easily, reliably, and quickly, and simplification of the production system and cost reduction can be achieved. Further, according to the vacuum processing using the present invention, the processing results are less scattered between lots, and a stable vacuum processing is always possible.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing an example of a vacuum processing apparatus according to the present invention.

FIG. 2 is a schematic configuration diagram illustrating an example of a vacuum processing apparatus according to the present invention.

FIG. 3 shows a VHF plasma CV using a frequency in a VHF band.
It is a schematic block diagram which showed an example of the manufacturing apparatus of the electrophotographic light-receiving member by the D method.

FIG. 4 is a schematic configuration diagram showing an example of a vacuum processing apparatus according to the present invention.

FIG. 5 is a schematic configuration diagram showing an example of a vacuum processing apparatus according to the present invention.

FIG. 6 is a diagram showing an example of a layer configuration of an electrophotographic light-receiving member that can be formed according to the present invention.

FIG. 7 is a schematic configuration diagram showing an example of a reaction vessel section of a vacuum processing apparatus that can be used in the present invention.

FIG. 8 is a schematic configuration diagram showing an example of a reaction vessel section of a vacuum processing apparatus that can be used in the present invention.

FIG. 9 is a schematic configuration diagram illustrating an example of an apparatus for manufacturing an electrophotographic light-receiving member by an RF plasma CVD method using an RF band frequency.

FIG. 10 shows a VHF plasma C using a VHF band frequency.
It is a schematic block diagram which showed an example of the manufacturing apparatus of the electrophotographic light-receiving member by the VD method.

FIG. 11 shows VHF plasma C using VHF band frequency.
It is a schematic block diagram which showed an example of the manufacturing apparatus of the electrophotographic light-receiving member by the VD method.

[Description of Signs] 101: movable reaction vessel section 102: exhaust section 103: connection section 104: reaction vessel side connection flange 105: exhaust section connection flange 106: reaction vessel 107: exhaust section 108: vacuum sealing valve 109 : Vacuum sealing valve 110: Vacuum sealing material 111: Opening 112: Opening 113: Dolly 2100: Deposition device 2101: Reaction vessel 2111: Cathode electrode 2112: Cylindrical base 2113: Support 2114: Raw material gas introduction pipe 2115: Matching box 2116: source gas pipe 2117: reaction vessel leak valve 2118: main exhaust valve 2119: vacuum gauge 2200: source gas supply device 2211 to 2216: mass flow controller 2221 to 2226: source gas cylinder 2231 to 2236: source gas cylinder valve 224 2246: Gas inflow valve 2251 to 2256: Gas outflow valve 2261 to 2266: Pressure regulator 301: Reaction vessel 302: Cathode electrode 303: High frequency power supply 304: Matching box 305: Cylindrical substrate 306: Film forming space 307: Heating element 308: Rotating shaft 309: Motor 310: Reduction gear 311: Exhaust pipe 312: Source gas supply means 400: Reaction vessel 401: Cylindrical base 402: High frequency power supply means 403: High frequency power supply 404: Matching box 405: Exhaust pipe 406: Rotating shaft 501: Reaction vessels 502, 506: Cathode electrode 503, 514: High-frequency power supply 504, 513: Matching box 505: Cylindrical substrate 507: Heating element 508: Rotating shaft 509: Motor 510: Reduction gear 511: Exhaust pipe 512: Source gas supply Means 601: Movable reaction vessel section 602: Connection flange 603: Reaction vessel 604: Vacuum sealing valve 605: Exhaust section 606: Vacuum sealing material 607: Opening section 608: Opening section 609: Dolly 700: Electrophotographic photosensitive member 701 : Support 702: photoconductive layer 703: surface layer 704: charge injection blocking layer 705: charge generation layer 706: charge transport layer 801: exhaust pipe 901: reaction vessel 902: cathode electrode 903: high frequency power supply 904: matching box 905: Cylindrical substrate 907: Heating element 908: Rotating shaft 909: Motor 910: Reduction gear 911: Exhaust pipe 912: Source gas supply means

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiyasu Shirasuna 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Takashi Otsuka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Tatsuyuki Aoike 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kazutaka Akiyama 3-30-2, Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (44)

[Claims] 1. A reaction vessel which can be decompressed, means for supplying an active gas into the reaction vessel, and exhaust means for depressurizing the reaction vessel, wherein an opening provided in the reaction vessel is provided. In a vacuum processing apparatus in which a member to be formed and a member to form an opening provided in the exhaust unit communicate with each other, the opening diameter of the opening provided in the reaction vessel is equal to the diameter of the opening provided in the exhaust unit. A vacuum processing apparatus characterized by being smaller than an opening diameter. 2. The apparatus according to claim 1, wherein said member forming said opening provided in said reaction vessel has a cylindrical shape.
The vacuum processing apparatus according to item 1. 3. The apparatus according to claim 1, wherein said member forming said opening provided in said exhaust means has a cylindrical shape.
The vacuum processing apparatus according to item 1. 4. The exhaust device according to claim 1, wherein said opening provided in said exhaust means is provided in an outer frame of said exhaust means.
The vacuum processing apparatus according to item 1. 5. The vacuum processing apparatus according to claim 1, wherein said member forming said opening provided in said reaction vessel has a flange. 6. The vacuum processing apparatus according to claim 1, wherein said member forming said opening provided in said exhaust means has a flange. 7. The vacuum processing apparatus according to claim 1, wherein said vacuum processing apparatus is a deposited film forming means for forming a deposited film on a substrate housed in said reaction vessel. 8. A method according to claim 7, wherein said deposited film forming means is a deposited film forming means by a plasma CVD method.
The vacuum processing apparatus according to item 1. 9. The vacuum processing apparatus according to claim 8, wherein said means for forming a deposited film by plasma CVD includes means for applying high-frequency power having a frequency of 50 to 450 MHz. 10. The vacuum processing apparatus according to claim 1, wherein said vacuum processing apparatus is an electrophotographic photoreceptor forming apparatus. 11. A member forming an opening provided in a reaction vessel capable of reducing pressure and a member forming an opening provided in exhaust means communicate with each other, and the exhaust means removes the reactive gas supplied into the reaction vessel. In the vacuum processing method of evacuating, a diameter of the opening of the member forming the opening provided in the reaction vessel is larger than an opening diameter of the opening of the member forming the opening provided in the evacuation unit. A vacuum processing method characterized by being small. 12. The vacuum processing method according to claim 11, wherein the member forming the opening provided in the reaction vessel has a cylindrical shape. 13. The vacuum processing method according to claim 11, wherein said member forming said opening provided in said exhaust means has a cylindrical shape. 14. The vacuum processing method according to claim 11, wherein said opening provided in said exhaust means is provided in an outer frame of said exhaust means. 15. The vacuum processing method according to claim 11, wherein the member forming the opening provided in the reaction vessel has a flange. 16. The vacuum processing method according to claim 11, wherein said member forming said opening provided in said exhaust means has a flange. 17. The vacuum processing method according to claim 11, wherein said vacuum processing method includes a deposited film forming step of forming a deposited film on a substrate housed in said reaction vessel. 18. The method according to claim 18, wherein said depositing film forming step is performed by plasma CVD.
The vacuum processing method according to claim 17, wherein the vacuum processing method is used. 19. The vacuum processing method according to claim 18, wherein in the step of forming a deposited film by the plasma CVD method, plasma is formed using high-frequency power having a frequency of 50 to 450 MHz. 20. The vacuum processing method according to claim 11, wherein said vacuum processing step is a step of forming a photoconductor for electrophotography. 21. A vacuum processing apparatus comprising: a reaction vessel capable of reducing pressure; A smaller diameter than the opening diameter of the exhaust means connected to the vacuum processing apparatus. 22. A vacuum processing method wherein the evacuation means reduces the pressure of a reaction vessel capable of reducing pressure through an opening on the reaction vessel side, wherein the opening diameter on the reaction vessel side is connected to the opening on the reaction vessel side. A vacuum processing method characterized in that the diameter is smaller than the opening diameter on the exhaust means side. 23. A vacuum processing apparatus having a reaction vessel capable of reducing pressure and an exhaust means for reducing pressure through an opening on the reaction vessel side, wherein the opening diameter on the reaction vessel side is the opening diameter on the reaction vessel side. A vacuum processing apparatus having a diameter different from the opening diameter of the exhaust unit connected to the vacuum processing means. 24. The vacuum processing apparatus according to claim 23, wherein said vacuum processing apparatus has means for supplying an active gas into said reaction vessel. 25. A member for forming the opening provided on the side of the reaction vessel, having a cylindrical shape.
4. The vacuum processing apparatus according to 3. 26. The vacuum processing apparatus according to claim 23, wherein the member forming the opening provided on the exhaust means side has a cylindrical shape. 27. An opening provided on the exhaust means side is provided in an outer frame of the exhaust means.
4. The vacuum processing apparatus according to 3. 28. The vacuum processing apparatus according to claim 23, wherein the member forming the opening provided on the reaction vessel side has a flange. 29. A member for forming an opening provided on the exhaust means side has a flange.
4. The vacuum processing apparatus according to 3. 30. The vacuum processing apparatus according to claim 23, wherein said vacuum processing apparatus is a deposited film forming means for forming a deposited film on a substrate housed in said reaction vessel. 31. A method according to claim 31, wherein said deposited film forming means is plasma CVD.
31. The vacuum processing apparatus according to claim 30, wherein the vacuum processing apparatus is a deposition film forming unit by a method. 32. The vacuum processing apparatus according to claim 31, wherein said means for forming a deposited film by plasma CVD includes means for applying high-frequency power having a frequency of 50 to 450 MHz. 33. An apparatus according to claim 23, wherein said vacuum processing apparatus is an electrophotographic photosensitive member forming apparatus.
3. The vacuum processing apparatus according to any one of 2. 34. A vacuum processing method wherein the evacuation means reduces the pressure of a reaction vessel capable of reducing pressure through an opening on the reaction vessel side, wherein the opening diameter on the reaction vessel side is connected to the opening on the reaction vessel side. A vacuum processing method characterized in that the opening diameter is different from that of the exhaust means. 35. The vacuum processing method according to claim 34, wherein said vacuum processing method includes a step of supplying an active gas into said reaction vessel. 36. The member forming the opening provided on the side of the reaction vessel is cylindrical.
5. The vacuum processing method according to 4. 37. The vacuum processing method according to claim 34, wherein the member forming the opening provided on the exhaust means side has a cylindrical shape. 38. An opening provided on the exhaust means side is provided in an outer frame of the exhaust means.
5. The vacuum processing method according to 4. 39. The vacuum processing method according to claim 34, wherein the member forming the opening provided on the reaction vessel side has a flange. 40. A member for forming an opening provided on the exhaust means side has a flange.
5. The vacuum processing method according to 4. 41. The vacuum processing method according to claim 34, wherein said vacuum processing method includes a deposition film forming step of forming a deposition film on a substrate housed in said reaction vessel. 42. The method according to claim 42, wherein the step of forming the deposited film is performed by plasma CVD.
The vacuum processing method according to claim 41, wherein the vacuum processing method is used. 43. The vacuum processing method according to claim 42, wherein in the step of forming a deposited film by the plasma CVD method, plasma is formed using high-frequency power having a frequency of 50 to 450 MHz. 44. The vacuum processing method according to claim 34, wherein said vacuum processing step is a step of forming a photoconductor for electrophotography.