JPH09184075A - Plasma treatment and treating apparatus therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasma treating apparatus for producing adequate deposited films suitable for cleaning of parts. SOLUTION: A waste gas treating device of a film forming system and a waste gas treating device of an etching system are connected to a reaction vessel via a discharge system having a means for controlling the changeover of discharge routes. A means for removing cleaning gases is arranged via the means 2000 for controlling the changeover of the discharge routes in the discharge route for connecting this reaction vessel and the waste gas treating device of the etching system. The film formation is executed by connecting the reaction vessel to the discharge route of the waste gas treating device of the film forming system in the film forming stage by control of the means 2000 for controlling the changeover and, simultaneously, the means for removing the cleaning gases is regenerated by connecting the means for removing the cleaning gases to the waste gas treating device of the etching system. The reaction vessel is connected to the waste gas treating device of the etching gas system and the cleaning treatment is executed by controlling the changeover of the discharge routes to the means for removing the cleaning gases in a reaction vessel cleaning treatment stage.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention produces a deposited film particularly suitable as a semiconductor element such as a photoreceptive member for electrophotography, a solar cell, a line sensor for image input, an imaging device, and a TFT on a substrate by a plasma CVD method. The present invention relates to a method of manufacturing a deposited film and a manufacturing apparatus therefor, and more particularly to a plasma processing method and a processing apparatus suitable for cleaning the apparatus and parts.

[0002]

2. Description of the Related Art As one method of producing a deposited film, a CVD method using low-temperature plasma has been spotlighted. In this method, the reaction vessel is depressurized to a high vacuum, the raw material gas is introduced into the reaction vessel, high frequency is applied to decompose the raw material gas by glow discharge, and a deposited film is formed on a substrate arranged in the reaction vessel. Is applied to the production of, for example, an amorphous silicon film. An amorphous silicon film produced by using silane gas (SiH4) as a film forming source gas by this method has relatively few local material levels existing in the forbidden band of amorphous silicon, and valence electron control can be achieved by doping impurities. It is possible and possible to obtain an amorphous silicon electrophotographic photosensitive member having excellent characteristics, and studies are being continued. Japanese Examined Japanese Patent Sho 60-35
Japanese Patent Publication No. 059 discloses an electrophotographic light-receiving member in which hydrogenated amorphous silicon is applied to a photoconductive portion. Further, Japanese Patent Laid-Open No. 62-20874 discloses a plasma CVD method for producing such a light receiving member for electrophotography.
Discloses a deposited film forming apparatus. like this,
In the plasma processing apparatus, polysilane, an amorphous film or the like is deposited inside the vacuum container and the exhaust pipe after the deposited film is formed. Conventionally, deposits are removed by dry cleaning such as plasma etching, cleaning in an alkaline solution, or honing by sandblasting or glass bead spraying. Among them, cleaning by plasma etching is widely used because high throughput can be obtained and processing can be performed without exposing the vacuum container to the atmosphere.
Japanese Patent Application Laid-Open No. 59-142839 discloses a new deposit due to the reaction between the etching gas and the deposit by cleaning the inner wall of the reaction chamber by plasma etching using a mixed gas of CF4 and O2 as the etching gas. It is disclosed that the cleaning can be performed without any occurrence.
Further, Japanese Patent Application Laid-Open No. 3-157667 discloses a manufacturing method including a process of removing deposits in a processing tank by using ClF3 as an etching gas. Furthermore, JP-A-3-20
Japanese Patent No. 0261 discloses a manufacturing method including introducing a ClF3 gas to clean the reaction chamber and the surface of the substrate.

[0003]

The conventional cleaning method as described above has been carried out by diluting the etching gas with an inert gas or intermittently treating it in order to suppress an increase in load on the vacuum pump. In such a conventional method, the cleaning time is long and there is a big problem in production that the apparatus cost is increased. Further, the cleaning gas treatment time is greatly shortened by using a high concentration and high partial pressure of the etching gas used for cleaning the by-products generated after the formation of the functional deposition film by the vapor phase method such as plasma CVD method. Although it has been considered from the past, high-concentration, high-partial-pressure processing causes a large amount of the high-concentration etching gas to flow into the exhaust pump, and high-temperature fluorine compounds can flow in only with pump oil. However, there is a problem that the life of the pump is shortened. for that reason,
In the actual situation, the processing conditions had to be determined in the relationship between the pump maintenance time and the cleaning processing time. In particular, for device cleaning, a highly reactive gas such as ClF3 has been attracting attention as an etching gas for the purpose of shortening the processing time. There is a problem in that the characteristics of this gas cannot be utilized by being used.

Therefore, the present invention solves the above-mentioned problems, and by a gas phase method such as plasma CVD, a by-product containing silicon as a main component is efficiently cleaned in a short time with a small load on the apparatus. An object of the present invention is to provide a plasma processing method and a processing apparatus capable of inexpensively mass-producing a functional deposited film used for a photoreceptive member for electrophotography, a solar cell or the like by processing.

[0005]

In order to achieve the above-mentioned object, the present invention performs film formation by an exhaust system connected to the film forming system exhaust gas processing apparatus during the film forming process, and at the same time, etching system exhaust gas. The cleaning gas removing means arranged in the exhaust system is regenerated by an exhaust system connected to the processing apparatus. That is, the plasma processing method of the present invention is a plasma processing method comprising both a film-forming exhaust gas processing apparatus and an etching-based exhaust gas processing apparatus, in which the cleaning processing is performed by a high-concentration and highly reactive etching gas, The film-forming system exhaust gas treatment device and the etching system exhaust gas treatment device are connected to a reaction vessel through an exhaust system having an exhaust path switching control means,
A cleaning gas removing means is disposed in an exhaust path connecting the reaction container and the etching-type exhaust gas processing device via an exhaust path switching control means, and the reaction container is controlled by the switching control means during the film forming process. At the same time as performing film formation by connecting to the exhaust path of the film-forming system exhaust gas processing device, the cleaning gas removing means is connected to the etching system exhaust gas processing device to regenerate the cleaning gas removing means, and the reaction container cleaning process is performed. The process is characterized in that the reaction container is connected to the etching-type exhaust gas treatment device and the cleaning process is performed by controlling the exhaust passage switching to the cleaning gas removing means. Further, the switching control in the cleaning treatment step in the present invention is performed by connecting the etching system exhaust gas treatment device to the film formation system exhaust path from the start of cleaning to the end of cleaning in the film formation system exhaust pipe for cleaning processing. After cleaning the inside of the exhaust pipe, the cleaning process is effectively performed by switching to the exhaust path provided with the cleaning gas removing means. Further, in the present invention, switching to the exhaust system provided with the cleaning gas removing means can be controlled by monitoring the temperature of the exhaust system including the reaction container. The regeneration of the cleaning gas removing means can be performed by introducing an inert gas into the cleaning gas removing means. Furthermore, the plasma processing apparatus of the present invention is provided with both a film forming system exhaust gas processing apparatus and an etching system exhaust gas processing apparatus, in a plasma processing apparatus configured to perform a cleaning process by a highly reactive and highly reactive etching gas, An exhaust path connecting the film forming system exhaust gas processing apparatus and the etching system exhaust gas processing apparatus to the first exhaust means and the reaction vessel through an exhaust system having an exhaust path switching means, the etching system exhaust gas processing apparatus and the reaction vessel. And an exhaust path having a second exhaust means in which cleaning gas removing means is disposed, an exhaust path having the first exhaust means, and an exhaust path having the second exhaust means. It is characterized by having an exhaust path connected through an exhaust path switching means. In the present invention, the switching control between the exhaust path having the first exhaust means and the exhaust path having the second exhaust means is provided in the temperature monitor provided in the reaction vessel and the exhaust pipe. It can be configured to be controlled by the temperature monitor provided and the temperature monitor provided in the means.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been made based on the following knowledge obtained by the present inventor.
That is, in the cleaning method of the by-product generated at the time of forming the deposited film by the vapor phase method such as the plasma CVD method as described above, C having high reactivity introduced into the reaction container is used.
The mixed gas of IF3 and the inert gas can be decomposed and cleaned by the discharge energy, but the cleaning speed is different due to the capacity of the reaction vessel and the exhaust pipe, and the processing time is extremely long for uniform processing. It was
Therefore, we tried to increase the concentration of ClF3 to shorten the cleaning time, but the by-product and unreacted ClF3 gas flow directly into the exhaust pump, which increases the load on the exhaust pump and replaces the hump in a short time. There was a problem of being forced to. Therefore, in order to solve such a problem, the method for reducing the load on the exhaust means and the cleaning time has been earnestly studied, and when cleaning with a high-concentration ClF3 gas, C is placed between the reaction container and the pump.
As a result of investigating the provision of the 1F3 gas removing means, it became clear that the load on the pump is extremely reduced by installing the molecular sieve, the cryopump, the dry scrubber, and the like.

However, the problem that the amount of gas that can be removed due to adsorption is limited, and the new problem that the by-product accumulated in the exhaust pipe must be removed is also clarified. It was Therefore, in view of such problems, the present invention has found that the molecular sieve and the cryopump are regenerated during the film formation process so that the film formation and cleaning can be continuously performed. When the cleaning starts, the cleaning process is performed in the same exhaust path as in the film formation at the start of cleaning, and after the cleaning in the exhaust pipe is completed, a cleaning gas removing means is provided in the exhaust path between the reaction container and the exhaust means. It has been found that it may be arranged to switch to the exhaust path and continue cleaning. Furthermore, since the temperature of the exhaust pipe and pump part suddenly rises at the end of cleaning the exhaust pipe,
It became clear that the load on the pump can be further reduced by controlling the switching of the exhaust path by monitoring this temperature. By adopting such an exhaust system configuration, the load on the pump is significantly reduced, the cleaning time is shortened and the pump maintenance is prolonged, and the film-cleaning one cycle time is shortened and long-term continuous operation is achieved. It has been found that the operation becomes possible and the manufacturing cost can be significantly reduced, and the present invention has been completed.

The contents of the present invention will be described below in more detail with reference to the drawings. FIG. 1 is a schematic configuration diagram showing an example of an apparatus for producing a photoreceptive member for electrophotography by a high frequency plasma CVD method (hereinafter abbreviated as “RF-PCVD”) using an RF band frequency as a power source. The structure of the manufacturing apparatus shown in FIG. 1 is as follows. This apparatus is roughly classified into a deposition apparatus (1100), a source gas supply apparatus (1200),
It is composed of an exhaust means (not shown) for reducing the pressure inside the reaction vessel (1111). Deposition device (110
In the reaction vessel (1111) in (0), the cylindrical support (1
112), a heater for heating the support (1113), a source gas introduction pipe (1114), and a high frequency matching box (1115) is connected. The source gas supply device (1200) uses SiH4, GeH4, H2, CH
4, cylinders of raw material gas such as B2H6, PH3 (1221-1
226) and valves (1231-1236, 1241-1)
246, 1251 to 1256) and a mass flow controller (1211 to 1216), and a cylinder of each source gas is connected to a gas introduction pipe (1114) in the reaction container (1111) via a valve (1260). The etching gas supply device (1300) is ClF.
It has the same configuration as the raw material gas supply device (1200) in which the raw material gas cylinders such as 3 are connected.

The production of a deposited film using this apparatus can be performed, for example, as follows. First, the reaction vessel (1
111), a cylindrical support (1112) is installed, and the reaction vessel (1
The inside of 111) is exhausted. Subsequently, the temperature of the cylindrical support (1112) is controlled to a predetermined temperature of 200 ° C. to 350 ° C. by the support heating heater (1113). In order to flow the raw material gas for deposit film formation into the reaction vessel (1111), it is necessary to confirm that the gas cylinder valve (1231 to 1237) and the reaction vessel leak valve (1117) are closed. (1241-1246),
Outflow valve (1251-1256), auxiliary valve (12
After confirming that 60) is opened, first, the main valve (1118) is opened to evacuate the reaction vessel (1111) and the gas pipe (1116). Next, the vacuum gauge (111
When the reading of 9) becomes about 5 × 10 ⁻⁶ Torr, the auxiliary valve (1260) and the outflow valve (1251 to 125
6) Close. Then, the gas cylinder (1221-122)
From (6), each gas is introduced by opening the valve (1231 to 1236), and the pressure of each gas is adjusted to ² Kg / cm ² by the pressure adjuster (1261 to 1266). Next, the inflow valves (1241 to 1246) are gradually opened to introduce the respective gases into the mass flow controllers (1211 to 1216).

After the preparation for film formation is completed as described above, each layer is manufactured by the following procedure. Cylindrical support (1
When the temperature of (112) reaches a predetermined temperature, the outflow valve (1
251 to 1256) and the auxiliary valve (1260) are gradually opened, and the gas cylinder (1221 to
1226) introduces a predetermined gas into the reaction vessel (1111) through the gas introduction pipe (1114). Next, the mass flow controllers (1211 to 1216) are adjusted so that each raw material gas has a predetermined flow rate. And
An RF power source (not shown) having a frequency of 13.56 MHz is set to a desired power, and a high frequency matching box (111)
RF power is introduced into the reaction vessel (1111) through 5) to cause glow discharge. The raw material gas introduced into the reaction vessel is decomposed by this discharge energy, and a predetermined deposited film containing silicon as a main component is formed on the cylindrical support (1112). At this time, in order to further increase the film thickness in the circumferential direction and the uniformity of the film characteristics, it is also effective to rotate at a desired rotation speed by a support rotating motor (not shown). After the formation of the desired film thickness, the supply of the RF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.
By repeating the same operation a plurality of times, a desired light-receiving layer having a multilayer structure is produced.

In the present invention, the source gases used for forming the deposited film are silane (SiH4) and disilane (S).
i2H6), silicon tetrafluoride (SiF4), disilicon hexafluoride (S
It is also effective to use an amorphous silicon forming raw material gas such as i2F6) or a mixed gas thereof. Diluent gas is hydrogen (H2), argon (Ar), helium (He)
Etc. are also effective. Further, as a characteristic improving gas for changing the band gap width of the deposited film, nitrogen (N
2), elements containing nitrogen atoms such as ammonia (NH3), oxygen (O2), nitric oxide (NO), nitrogen dioxide (NO)
2), dinitrogen oxide (N2O), carbon monoxide (CO), carbon dioxide (CO2), and other elements containing oxygen atoms, methane (CH
4), hydrocarbons such as ethane (C2H6), ethylene (C2H4), acetylene (C2H2), propane (C3H8), fluorine compounds such as germanium tetrafluoride (GeF4) and nitrogen fluoride (NF3), or a mixed gas thereof. It is effective to use together. Further, in the present invention, even if dopant gases such as diborane (B2H6), boron fluoride (BF3) and phosphine (PH3) are simultaneously introduced into the discharge space for the purpose of doping, the present invention is similarly effective. is there.

In the present invention, the effect was recognized in any region of the pressure of the discharge space during the deposition of the deposited film.
From 05 torr to 5.0 torr, preferably from 0.1 torr to 2.0 torr, particularly good results in terms of discharge stability and deposited film uniformity were obtained with good reproducibility. In the present invention, the substrate temperature during the deposition of the deposited film is effective in the range of 100 ° C. or higher and 500 ° C. or lower, but particularly 150 ° C. or higher and 450 ° C. or lower, preferably 200 ° C. or higher and 400 ° C. or lower, and most preferably A remarkable effect was confirmed at temperatures above 250 ° C and below 350 ° C. In order to clean the apparatus in the present invention, a dummy cylinder is inserted after the support is taken out, an etching gas is introduced instead of the raw material gas, and a plasma etching process is performed.

FIG. 2 shows an example of the device configuration of the present invention. The reaction vessel is connected to the pipe (2012), and passes through the first stop valve (2001) to the first exhaust pump (2007),
A three-way switching valve (2006) is used to form a film forming system exhaust gas treatment device (2010) and an etching system exhaust gas treatment device (201).
1) is connected. Further, the exhaust pipe (2012) connected to the reaction vessel is connected to the second stop valve (200
2) and is connected to the cleaning gas removing means (2009), and a third stop valve (2003) is provided between the cleaning gas removing means and the first exhaust hoop (2007).
And a fifth stop valve (2005) is installed between the second exhaust pump (2008). The second exhaust pump (2008) is connected to the etching system exhaust gas treatment device (2011). On the upstream side of the cleaning gas removing means (2009), a fourth stop valve (2004) for introducing an inert gas is provided in addition to the second stop valve (2002).

When forming the deposited film, the first stop valve (2001) is opened and the first exhaust pump (200) is opened.
7), the three-way switching valve (2006) is set to allow the exhaust gas to flow into the film-forming system exhaust gas treatment apparatus (2010). At that time, the second and third stop valves (20
02, 2003) closed and the fourth stop valve (20
04) to remove the inert gas from the cleaning gas (2)
009), the fifth stop valve (2005)
After that, the exhaust gas is exhausted by the second exhaust pump (2008) and the exhaust gas is caused to flow through the etching system exhaust gas treatment device (2011) to regenerate the cleaning gas removing means (2009). When cleaning, first, only the first stop valve (2001) is opened and the three-way switching valve is opened from the first exhaust pump (2007) to the etching system exhaust gas treatment device (2011) as in film formation. Connect to. Exhaust pipe (2012) and first exhaust pump (2
The end of processing in the exhaust pipe is recognized based on the value of the temperature monitor provided in (007). After that, the first stop valve (2001) is closed and at the same time, the second stop valve (2002) and the third stop valve (2003) are opened, cleaning of the pipe in the branch portion is promoted, and the reaction container and the exhaust pipe are connected. (2012) and cleaning is performed while continuing to monitor the temperature of the first pump. Further, it is more effective to connect the temperature monitor values to the central processing unit so as to be sequentially input, and to comprehensively judge the gas flow rate, discharge power, etc. to control the exhaust path.

As the etching gas, for example, CF4,
A mixed gas of CF4 and O2, ClF3, a mixed gas of ClF3 and an inert gas, and the like are used. Further, it is preferable to use ClF3 gas as the ClF3 gas because it is possible to perform an efficient cleaning process without plasma conversion. He, Ne and Ar are preferable as the inert gas introduced at the same time as the ClF3 gas used in the present invention. As the cleaning gas removing means used in the present invention, it is possible to use a cryopump as a trap, a molecular sieve, a dry scrubber, or any other material that adsorbs and removes gas and that can efficiently remove fluoride. it can.

In the present invention, the pressure in the apparatus for cleaning by plasma etching is 0.1 T.
orr or more and 400 Torr or less, preferably 0.3T
It is preferable to adjust and control the plasma so that it spreads in the entire apparatus at a pressure of not less than orrr and not more than 100 Torr. Further, it is also effective to change the internal pressure during the processing step in order to efficiently clean the whole. In the present invention, the discharge power input to generate plasma is
In the case of a high frequency (RF), 1000 W or more and 3000 W or less, in the case of VHF band, 800 W or more and 2000 W or less, and when using microwaves, 500 W or more and 2000 W or less are preferable, and it is preferable to appropriately adjust so as to stabilize the discharge. These conditions are not items that are uniquely determined, but items that are comprehensively determined and selected including the device configuration, gas flow rate, and the like.

Experimental examples and examples of the present invention will be described below, but the present invention is not limited thereto. Experimental Example First, an experimental example of the present invention will be described. The deposited film forming apparatus shown in FIG. 1 was used to form an amorphous silicon deposited film on the cylindrical substrate under the conditions shown in Table 1 to produce a blocking type electrophotographic photoreceptor having the layer structure shown in FIG. As the cleaning gas removing means, a device that operates a cryopump as a trap was used. Then, as shown in Table 2, cleaning was performed by changing the internal pressure and the discharge power with the ClF3 / (ClF3 + inert gas) value set to 75%. However, in the exhaust path at that time, only the first stop valve is opened and the first exhaust pump 1 exhausts air as in the conventional case. The temperature of the pump was monitored, and when the rapid temperature rise was detected, the cleaning was completed. At the end of
The cleaning completion status in the reaction container and the exhaust pipe and the time until the cleaning was completed were evaluated. ClF3 / (Cl
F3 + inert gas) value was 25% and the condition when cleaning was evaluated as a standard. For comparison, under the same conditions, the same evaluation was performed when cleaning was performed by a conventional apparatus, and the results are shown in Table 4.

<Evaluation of Cleaning Completion Status> ∘: There is no problem as it is exactly the same as the normal status. Δ: Some residue remains, but there is no problem in practical use. ×: There are many residues and cleaning is not completed. <DE time> When the ClF3 / (ClF3 + inert gas) value is 25%, the time required to complete the cleaning is 1
The value was set to 00% and indicated as a relative value for that time. <Deterioration status of vacuum pump> The deterioration status of the rotary pump oil used as a part of the exhaust means was examined. Regarding the deterioration condition of oil, the results of comprehensive evaluation of the pumping capacity (achieved vacuum level) and the oil viscosity after 30 cycles of film formation and cleaning as one cycle are based on the following criteria. evaluated. ◯ ・ ・ ・ It is exactly the same as the normal state and there is no problem. Δ: Deterioration is slightly advanced, but there is no problem in practical use. X: Deteriorated severely and needs to be replaced. <Operation status of cleaning removal means> The operation status of the cleaning removal means was confirmed. The operation status of the cleaning removing means is as follows.
The evaluation was made by the difference in time until the temperature of the pump at the 0th cycle rose sharply. The regeneration process of the cleaning removal means is H
Evacuation was performed for about 4 hours while introducing e-gas (500 SCCM). ○: Almost no change. △ ・ ・ ・ Slightly faster in the 30th cycle,
No problem in practical use. × ... The temperature of the 30th cycle rises quickly and the cleaning is not completed.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3] Even in the DE7 cycle, by extending the regeneration time of the cleaning gas removing means, the deterioration of the pump and the operating state of the cleaning gas removing means are exactly the same as in the normal state in the process of 30 cycles, and there is no problem. I understood.

[0022]

[Table 4] If the removal device is not installed, if the etching gas is at a high concentration, the pump deteriorates quickly and before cleaning is completed,
I had to stop cleaning.

[0023]

Embodiments of the present invention will be described below. Example 1 An electrophotographic photosensitive member having a layer structure shown in FIG. 3 was prepared by using a cylindrical substrate made of aluminum and having a diameter of 108 mm, a length of 358 mm, and a wall thickness of 5 mm under the conditions shown in Table 5 using the apparatus shown in FIG. Then, cleaning was performed under the conditions shown in Table 6. At that time, based on the result of measuring the temperature by the exhaust pipe (2012), the substrate heating heater (1113), and the temperature monitor attached to each pump, the timing of switching the exhaust path is changed at each point shown in FIG. Then, the cleaning condition in the reaction vessel and the exhaust pipe was compared with the pump deterioration condition. The treatment times were all the same (50 minutes). In addition, cleaning was completed at each point and the cleaning status at that time was confirmed. A cryopump was used as the cleaning gas removing means.

[0024]

[Table 5]

[0025]

[Table 6] Point A is the point where the temperature of the exhaust pipe starts to rise sharply, Point B is the point where the temperature of the first exhaust pump (pump 1) begins to rise sharply, Point C is the point where the temperature rise in the exhaust pipe has ended, and Point D is the reaction. This is the point where the temperature of the container begins to rise sharply.

[0026]

[Table 7] <Cleaning status> ◯ ・ ・ ・ There is no problem as it is exactly the same as the normal status. Δ: Some residue remains, but there is no problem in practical use. ×: There are many residues and cleaning is not completed. <Degradation status> ◯ ・ ・ ・ It is exactly the same as the normal state and there is no problem. Δ: Deterioration is slightly advanced, but there is no problem in practical use. X: Deteriorated severely and needs to be replaced. From the above results, it can be seen that both the completion of cleaning and the prevention of deterioration of the pump can be achieved by recognizing that the temperature of the first pump has started to rapidly rise and switching the exhaust path. The completion of the entire cleaning was completed at point E, at which the temperature of the reaction vessel rapidly increased and the temperature of the exhaust pipe subsequently increased rapidly. That is, in the cleaning process, at the point where the temperature of the first pump started to rise rapidly, the process was switched to the second pump to continue the process, and at the point where the temperature of the reaction container began to rise rapidly, the cleaning gas removing means was arranged. It can be seen that by switching to piping, the cleaning processing speed can be improved while preventing deterioration of the pump.

[Example 2] Using the same substrate as in Example 1 and using the same apparatus as in Example 1, an electrophotographic photosensitive member having a four-layer structure was prepared under the conditions shown in Table 8 and the same as in Example 1. Cleaning was performed under the conditions. It has been found that the present invention is also effective for cleaning after the production of the electrophotographic photoconductors having different layer constitutions produced in this way.

[0028]

[Table 8] [Example 3] Using the same substrate as in Example 2, an electrophotographic photosensitive member similar to that in Example 2 was prepared, and cleaning was performed under the same conditions as in Example 1. However, the cleaning gas removing means used was one in which molecular sieves were connected in two stages. Film formation and cleaning were repeated 30 cycles, and the device stability at that time was also evaluated. The molecular sieve was regenerated for 5 hours by heating while introducing an inert gas during the film forming process. As a result, it was found that the present invention is effective when a molecular sieve is used as the cleaning gas removing means.

Example 4 Using the same substrate as in Example 2, an electrophotographic photosensitive member similar to that in Example 2 was prepared and cleaned under the same conditions as in Example 1. However, a dry scrubber was used as the cleaning gas removing means. Film formation and cleaning were repeated 30 cycles, and the device stability at that time was also evaluated. The dry scrubber has a structure in which the adsorbent can be replaced during the film formation process. As a result,
It has been found that the present invention is also effective when a dry scrubber is used as the cleaning gas removing means.

Example 5 Using the same substrate as in Example 2, an electrophotographic photosensitive member similar to that in Example 2 was prepared and cleaned under the cleaning conditions shown in Table 9. As the cleaning gas removing means, a cryopump, a molecular sieve, and a dry scrubber were arbitrarily changed to perform cleaning. Film formation and cleaning were repeated 30 times, and the stability of the apparatus at that time was also evaluated. As a result, it was found that the present invention is effective regardless of the cleaning gas removing means.

[0031]

[Table 9] [Example 6] Using the apparatus shown in Fig. 3, the substrate holder used for producing the electrophotographic photosensitive members in Examples 1 to 6 was cleaned. A method of introducing only etching gas without introducing high frequency is adopted. The cleaning conditions are shown in Table 10. A cryopump was used as the cleaning gas removing means. Repeat cleaning 30 cycles,
The device stability at that time was also evaluated. As a result, it was found that the present invention is effective even with such a system.

[0032]

[Table 10] [Example 7] Using the apparatus shown in Fig. 3, the substrate holder used for producing the electrophotographic photosensitive members in Examples 1 to 6 was cleaned. A method of introducing only etching gas without introducing high frequency is adopted. The cleaning conditions are shown in Table 11. A molecular sieve was used as a cleaning gas removing means. The cleaning was repeated 30 cycles, and the stability of the apparatus at that time was also evaluated. As a result,
It has been found that the present invention is effective even with such a system.

[0033]

[Table 11]

[0034]

As described above, according to the present invention, during the film forming process, the film formation is performed by the exhaust system connected to the film forming system exhaust gas treatment apparatus, and at the same time, the exhaust system connected to the etching system exhaust gas treatment apparatus is formed. By regenerating the cleaning gas removing means arranged in this exhaust system, it is possible to efficiently perform a cleaning process with less load on the apparatus in a short time, such as a photoreceptive member for electrophotography or a solar cell. It is possible to mass-produce the functional deposited film used for the above at low cost. Also,
According to the present invention, the cleaning process is performed in the exhaust path at the time of film formation at the start of cleaning, and after the cleaning of the inside of the exhaust pipe is completed, the exhaust path having the cleaning gas removing means is switched to and the cleaning is continued. Accumulated by-products can be efficiently removed. Further, the present invention controls the switching to the exhaust path having the cleaning gas removing means by a temperature monitor provided in the reaction container, a temperature monitor provided in the exhaust pipe and a temperature monitor provided in the means. By doing so, it becomes possible to perform a cleaning process that can further reduce the load on the pump.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of an example of the apparatus of the present invention, which is an apparatus for producing a light receiving member for electrophotography by a glow discharge method using a high frequency in an RF band.

FIG. 2 is an exhaust pipe diagram having a cleaning gas removing means of the present invention.

FIG. 3 is an example of a cleaning container of the present invention.

FIG. 4 is an example of a transition of a temperature monitor and an exhaust path control point during a cleaning process of the present invention.

[Explanation of symbols]

 1100 Deposition apparatus 1111 Reaction vessel 1112 Cylindrical support 1113 Support heating heater 1114 Raw material gas introduction pipe 1115 Matching box 1116 Raw material gas pipe 1117 Reaction vessel leak valve 1118 Main exhaust valve 1119 Vacuum gauge 1200 Raw material gas supply apparatus 1211 to 1216 Mass flow Controller 1221 to 1226 Raw material gas cylinder 1231 to 1236 Raw material gas cylinder valve 1241 to 1246 Gas inflow valve 1251 to 1256 Gas outflow valve 1261 to 1266 Pressure regulator 1300 Etching gas supply device 2000 Exhaust path switching unit 2001 to 2005 Stop valve 2007 First exhaust Pump 2008 Second exhaust pump (regeneration only) 2106 3-way switching valve 2109 Cleaning gas removal Means 2110 deposition system exhaust gas treatment apparatus 2111 etching system exhaust gas processing system 2112 reactor exhaust pipe 2113 inert gas inlet pipe 3000 cleaning apparatus 3001 vacuum container 3002 etching gas jet pipe 3003 stirring blade 3004 exhaust pipe (connection in Fig. 2)

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display area H01L 31/042 H01L 31/04 R

Claims (6)

[Claims] 1. A plasma processing method comprising both a film-forming exhaust gas processing device and an etching-based exhaust gas processing device, wherein a cleaning process is carried out with an etching gas having a high concentration and high reactivity, wherein the film-forming exhaust gas is used. The processing device and the etching-type exhaust gas processing device are connected to a reaction vessel through an exhaust system having an exhaust path switching control means, and an exhaust path switching control means is connected to an exhaust path connecting the reaction container and the etching-type exhaust gas processing device. A cleaning gas removing unit is disposed via the above, and during the film forming process under the control of the switching control unit, the reaction container is connected to the exhaust path of the film forming system exhaust gas treatment apparatus to perform film formation, and Connecting the cleaning gas removing means to the etching type exhaust gas treatment device to regenerate the cleaning gas removing means,
A plasma processing method characterized in that, in the reaction vessel cleaning treatment step, the reaction vessel is connected to the etching-type exhaust gas treatment device and a cleaning treatment is performed by controlling an exhaust passage switching to a cleaning gas removing means. 2. The exhaust path switching control in the cleaning processing step is performed by connecting the etching system exhaust gas processing apparatus to the film forming system exhaust path from the start of cleaning to the end of cleaning in the film forming system exhaust pipe. The plasma processing method according to claim 1, wherein a cleaning process is performed, and after the cleaning of the inside of the exhaust pipe is completed, the cleaning process is performed by switching to an exhaust path in which the cleaning gas removing unit is arranged. 3. The plasma processing method according to claim 2, wherein the switching to the exhaust path provided with the cleaning gas removing means is performed by monitoring the temperature of the exhaust system including the reaction container. 4. The plasma processing method according to claim 2, wherein the cleaning gas removing means is regenerated while introducing an inert gas into the cleaning gas removing means. 5. A plasma processing apparatus comprising both a film-forming exhaust gas processing apparatus and an etching-based exhaust gas processing apparatus, wherein a cleaning process is carried out with an etching gas having a high concentration and high reactivity, wherein the film-forming exhaust gas is An exhaust path, in which the processing device and the etching-based exhaust gas processing device are connected to the first exhaust means and the reaction container via an exhaust system having an exhaust path switching means, and the etching-based exhaust gas processing device and the reaction container are connected to the exhaust path. An exhaust path having a second exhaust means in which a cleaning gas removing means is arranged,
A plasma processing apparatus, comprising: an exhaust path having the first exhaust means and an exhaust path having the second exhaust means, the exhaust path being connected via an exhaust path switching means. 6. An exhaust path switching control between an exhaust path having the first exhaust means and an exhaust path having the second exhaust means is provided in a temperature monitor provided in the reaction vessel and the exhaust pipe. 6. The plasma processing apparatus according to claim 5, wherein the temperature is controlled by a temperature monitor and a temperature monitor provided in the exhaust means.