JP2002256436A - Apparatus and method for forming deposited film by plasma CVD - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To significantly reduce the amount of polysilane deposited in an exhaust pipe, shorten cleaning processing time, reduce the amount of cleaning material used, reduce deterioration of an exhaust pump oil, and deteriorate an exhaust pump. To reduce SOLUTION: It has a reaction vessel 101, a substrate holder 105, a raw material gas introducing means 192, a substrate heating / heating means 106, a high frequency energy introducing means 110, an exhaust pipe 111, a ClF ₃ gas introducing means 138, and an exhaust pipe 111. A deposited film forming apparatus in which a heater 195 made of graphite is installed; and
Exhaust piping 1 by heater 195 made of graphite
11 A deposition film forming method in which a deposition film is formed while heating the inside, and a ClF ₃ gas is used for a cleaning process after the formation of the deposition film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a functional deposition film particularly suitable as a semiconductor element such as an electrophotographic photosensitive member, a solar cell, an image input line sensor, an imaging device, and a TFT on a substrate by a plasma CVD method. Device and method for doing so.

[0002]

2. Description of the Related Art Conventionally, amorphous silicon (hereinafter referred to as "a-Si") has been used as a functional deposition film used as a semiconductor element such as an electrophotographic photosensitive member, a solar cell, an image input line sensor, an imaging device, and a TFT. ), For example, an a-Si film compensated with hydrogen or / and halogen (fluorine, chlorine, etc.) has been proposed, and some of them have been put to practical use.

Various devices for forming such a functional deposited film have been proposed. They are, for example, those obtained by vacuum deposition, those obtained by ion plating, those obtained by thermal CVD, and the like. Among them, a film forming method under reduced pressure such as plasma CVD is preferably used in practice.

However, when a functional deposition film is formed on a predetermined substrate surface by these film forming methods, unreacted gas that has not become a functional deposition film is exhausted as an exhaust gas to an exhaust system. The by-product components therein cause a polymerization reaction inside the reactor or inside the exhaust pipe, and powdery by-products (hereinafter referred to as “polysilane”) accumulate inside the reactor or inside the exhaust pipe. Would. Then, the deposited polysilane naturally falls during the formation of the functional deposited film, or scatters due to a gas flow, backflow from an exhaust system, or the like, and is taken in as an impurity on the substrate or in the deposited film. If the characteristics are lowered or adhere to the surface of the base, defects such as pinholes are generated, and as a result, there is a problem that the yield is greatly reduced.

Therefore, conventionally, various methods have been proposed for suppressing polysilane deposited in a reaction furnace or an exhaust pipe when a functional deposition film is formed.

For example, Japanese Unexamined Patent Publication No. 60-114570 discloses that by heating an exhaust pipe and a powder trap, the powder is not a low-density soft fine powder, but a high-density hard fine powder that can be easily treated. The method of collecting as a sample is described. Japanese Patent Application Laid-Open No. 1-312833 discloses a method of completely decomposing gas that has not been thermally decomposed in a reaction section by providing a second reaction chamber and a heating means between an airtight container and an exhaust system. Has been described. Also, Japanese Patent Application Laid-Open No.
Japanese Patent No. 3889 describes a method in which an exhaust pipe is penetrated into a substrate heater and a film is deposited while heating the exhaust pipe. Japanese Patent Application Laid-Open No. 8-299784 discloses a method of thermally decomposing unreacted processing gas in exhaust gas by providing a heating trap means comprising a baffle plate in a trap passage container provided in the middle of the exhaust passage. And a method of trapping almost completely. Japanese Patent Application Laid-Open No. 8-2
In Japanese Patent No. 18174, a tape heater is provided around the outer periphery of an exhaust pipe, and a rubber heater is attached to an outer peripheral surface of a connecting member of the exhaust pipe, thereby preventing exhaust matter from adhering to the inside of the exhaust pipe and near a joint. A method is described.

With these techniques, a method has been established for efficiently collecting or treating powder or film fragments generated by a polymerization reaction of unreacted gas or reactive gas in an exhaust pipe when forming a functional deposited film. It has been.

In addition, the inside of the reaction vessel is cleaned in several film forming cycles or in each film forming cycle to remove polysilane deposited on a portion other than a target film forming portion (hereinafter referred to as “cleaning”). Is also performed. As one of the cleaning methods at that time, there is a dry etching (hereinafter, referred to as “DE”) process. Specifically, the cleaning raw material is introduced into the reaction vessel in a vaporized (gas) state,
The element is converted into an excited state by energy such as plasma, heat, light, or the like, and is reacted with the elements forming polysilane.

As cleaning materials used in the cleaning process, carbon tetrafluoride (CF ₄ ), nitrogen trifluoride (NF ₃ ), sulfur hexafluoride (SF ₆ ), chlorine trifluoride (C
lF ₃₎ and others as mentioned, in recent years, can decompose at low energy, highly reactive with the benefits of having a very high cleaning rate, chlorine trifluoride (ClF ₃₎ are attention, chlorine trifluoride Various cleaning treatment methods using (ClF ₃ ) in a vaporized (gas) state have been proposed.

For example, Japanese Patent Application Laid-Open No. Hei 10-81950 discloses that chlorine fluoride (Cl) having a concentration of 50 to 100% by volume is used.
F), chlorine trifluoride (ClF ₃ ), chlorine pentafluoride (Cl
A method of performing a cleaning process using F ₅ ) in a vaporized (gas) state is described. Also, JP-A-6-2143
In the publication, chlorine trifluoride (ClF ₃ ) is vaporized (gas).
A method of performing a cleaning process while sequentially reducing the gas concentration when used in a state is described. Japanese Patent Application Laid-Open No. H11-222680 discloses chlorine trifluoride (ClF).
A method is described in which when ₃ ) is used in a vaporized (gas) state, a plurality of temperature sensors are provided in a gas introduction path, and the condition of the cleaning process is set or controlled by an output signal thereof.

By these techniques, a method for efficiently and rapidly cleaning the inside of the reaction vessel or the inside of the exhaust pipe has been established.

FIG. 2 is a schematic vertical sectional view showing an example of a conventional apparatus for producing a deposited film by a high-frequency plasma CVD method.

This apparatus is roughly classified into a deposition apparatus (29
1), source gas supply device (292), reaction vessel (20)
1) It is composed of an exhaust device (293) for reducing the pressure inside.

In the reaction vessel (201), an Al cylindrical substrate (208), a cylindrical substrate holder (205) for holding the Al cylindrical substrate (208), a heating heater (206), A gas introduction pipe (207) is installed, and a high-frequency matching box (217) and a high-frequency power supply (210) are further connected. In addition, the reaction vessel (20
1) also serves as an electrode, and is composed of an upper lid (202), a base plate (203), an insulator (204) and the like.

The source gas supply device (292) includes silane (SiH ₄ ), germane (GeH ₄ ), hydrogen (H ₂ ), methane (CH ₄ ), diborane (B ₂ H ₆ ), phosphine (PH ₃ ) and the like. Raw material gas cylinders (231-
236) and a source gas cylinder valve (241) for forming a deposited film.
To 246), gas pressure regulators (281 to 286), source gas inflow valves for deposition film formation (251 to 256), source gas outflow valves for deposition film formation (261 to 266), and mass flow controllers (271 to 276) And the cylinder of the source gas for forming each deposited film is a valve (21).
5) The reaction vessel (2) is connected via the raw material gas pipe (209).
01) is connected to the gas introduction pipe (207) arranged in the inside.

A cleaning material gas cylinder (23)
7, 238) and a cleaning material gas cylinder valve (2
47, 248), gas pressure regulators (287, 288),
Cleaning material gas inflow valves (257, 258),
Cleaning material gas outflow valve (267, 268),
And a mass flow controller (277, 278), and a cylinder of each cleaning source gas is connected to a gas introduction pipe (207) arranged in the reaction vessel (201) via a valve (216).

The exhaust device (293) is connected to the reaction vessel (20).
The exhaust pipe (21) from 1) to the exhaust pump (294)
1), and a leak valve (212), a main valve (213), and a vacuum gauge (214) are also provided.

Using this apparatus, a functional deposition film containing silicon as a main component is formed on the surface of an Al cylindrical substrate (208). Then, the reaction vessel (20
A cleaning process is performed on the functional deposited film or polysilane generated and deposited inside 1) or inside the exhaust pipe (211). The method of forming and cleaning the functional deposited film can be performed as follows.

First, with the Al-made cylindrical substrate (208) set in the cylindrical-substrate holder (205) for holding the Al-made cylindrical substrate (208), a predetermined volume in the reaction vessel (201) is set. And the exhaust device (29
The inside of the reaction vessel (201) is evacuated according to 3).

Subsequently, the surface temperature of the Al cylindrical substrate (208) is set to 200 ° C. by the heater (206).
The temperature is controlled to a predetermined temperature of 400 ° C. to 400 ° C. When the surface temperature of the Al cylindrical substrate (208) reaches a predetermined temperature, the source gas cylinder valves (241 to 246) for forming a deposited film,
Source gas inflow valves (251 to 256) for forming a deposited film,
A necessary one of the deposited film forming source gas outflow valves (261 to 266) is opened, and a predetermined source gas is reacted from the deposited film forming source gas cylinder (231 to 236) via a gas introduction pipe (207). It is introduced into the container (201).

Next, a mass flow controller (271)
To 276), the source gas for forming each deposited film is adjusted to have a predetermined flow rate. At that time, the reaction vessel (201)
The exhaust device (293) is adjusted so that the internal pressure of the exhaust gas reaches a predetermined pressure of 133 Pa or less.

When the internal pressure is stable, the high-frequency power supply (21)
From 0), high-frequency energy is introduced into the reaction vessel (201) through the high-frequency matching box (217) to generate glow discharge. The discharge energy decomposes the raw material gas for forming a deposited film introduced into the reaction vessel (201), and a functional deposited film mainly containing predetermined silicon is formed on the surface of the Al cylindrical body (208). It is formed.

After forming a functional deposited film mainly containing predetermined silicon on the surface of the Al cylindrical substrate (208),
An Al cylindrical substrate (not shown) for cleaning is put in place of the 1 cylindrical substrate (208), and an exhaust device (29
According to 3), the inside of the reaction vessel (201) is evacuated to a predetermined pressure.

When a predetermined pressure is reached, the valve (216)
And open the cleaning material gas cylinder (237, 23
8) through the valve (216) to the reaction vessel (20).
1) A cleaning raw material gas is introduced from a gas introduction pipe (207) disposed inside.

When the cleaning raw material gas comes into contact with and reacts with the functional deposition film or polysilane, the decomposition process proceeds, and the inside of the reaction vessel (201) or the exhaust pipe (21) is decomposed.
The internal cleaning process of 1) is performed.

[0026]

In recent years, photoconductors for electrophotography have been made uniform in film thickness and film quality and have been improved in terms of yield. However, in order to improve overall characteristics, further improvements have been made. In fact, there is room to be done. In particular, high image quality, low cost, high speed, and high durability of an electrophotographic apparatus are rapidly progressing, and an optical exposure apparatus, a developing apparatus, a transfer apparatus, and the like in the electrophotographic apparatus in order to improve image characteristics. As a result of these improvements, there has been a demand for an electrophotographic photosensitive member that is less expensive than before.

As a method of reducing the cost of the electrophotographic photoreceptor, reduction of the cleaning material used in the cleaning process by reducing the cleaning process time, reduction of the frequency of changing the exhaust pump oil, maintenance of the exhaust pump, There is a method of reducing the replacement frequency and reducing the manufacturing cost.

However, the time required for the cleaning process is such that the longer the amount of polysilane deposited during the formation of the functional deposition film, the longer the time required for the cleaning process. Will increase. In addition, an increase in the amount of polysilane deposited inside the reaction vessel or the exhaust pipe causes exhaust resistance to cause a decrease in exhaust efficiency, and also shortens the life of the exhaust pump itself. There is also a problem that the replacement frequency increases. In addition, the amount of polysilane mixed in the exhaust pump increases, the deterioration of the exhaust pump oil is accelerated, and the frequency of oil replacement of the exhaust pump increases, thereby limiting the operation rate of the apparatus. There's a problem.

When the production capacity decreases due to the above factors,
Manufacturing costs increase. Therefore, in order to reduce the cost, it is necessary to reduce the amount of polysilane generated at the time of forming the deposited film.

An object of the present invention is to provide a plasma C as described above.
An object of the present invention is to solve the conventional problems when forming a functional deposition film by a deposition film forming apparatus using the VD method, and to form a functional deposition film satisfying the above-mentioned requirements.

That is, the main object of the present invention is to reduce the amount of polysilane deposited at the time of forming the functional deposition film, shorten the time required for the cleaning process, and reduce the amount of the cleaning material used for the cleaning process. It is an object of the present invention to provide a deposited film forming apparatus and a deposited film forming method.

A further object of the present invention is to provide a deposited film forming apparatus and a deposited film forming method capable of reducing the manufacturing cost by reducing the frequency of maintenance and replacement of the exhaust pump and the frequency of replacing the exhaust pump oil. To provide.

[0033]

SUMMARY OF THE INVENTION The present invention provides a reaction space comprising a vacuum-tight region, a substrate holder capable of placing a substrate for forming a deposited film in the reaction space, Source gas introduction means for introducing gas,
A heating means for heating the substrate, a high-frequency energy introducing means for introducing high-frequency energy into the reaction space to generate a glow discharge by exciting the source gas, and an exhaust pipe for exhausting the reaction space; In a deposition film forming apparatus by a plasma CVD method, chlorine trifluoride (Cl
F ₃ ) A deposition film forming apparatus comprising means for introducing a gas, and a heater made of graphite is installed inside the exhaust pipe.

Further, according to the present invention, a base is placed in a reaction space comprising a vacuum-tight region, and high-frequency energy is introduced into the reaction space while introducing a raw material gas into the reaction space and exhausting the reaction space. In the method of forming a deposited film by a plasma CVD method in which a glow discharge is generated by excitation of the source gas to form a deposited film, a graphite heater is used to exhaust the reaction space. The deposition film is formed while heating the inside of the exhaust pipe, and chlorine trifluoride (ClF ₃ ) gas is used for a cleaning process after the formation of the deposition film. Is the way.

In the present invention, the heating temperature (A) inside the exhaust pipe is preferably controlled within the range of 200 ° C. ≦ (A).

The following is a description of how the present inventors have completed the present invention as a result of intensive studies.

First, the present inventors heated the inside of the exhaust pipe when forming the functional deposition film, so that by-products in the unreacted gas which did not become the functional deposition film exhausted to the exhaust treatment system. A method in which the generated components are chemically changed into a film state or a gas (gas) state by a thermal CVD effect is adopted, and this can reduce the amount of polysilane deposited inside the exhaust pipe at the time of forming a functional deposition film. We thought and thought about it.

As a result, when forming the functional deposited film, a heater is installed as a heating means inside the exhaust pipe from the reaction vessel to the exhaust pump, and when the inside of the exhaust pipe is heated to 200 ° C. or higher, the exhaust pipe is heated. It has been found that the amount of polysilane deposited in the inside can be greatly reduced. That is, the temperature (A) for heating the inside of the exhaust pipe is 200
It has been found that it is preferable to control the temperature to be equal to or lower than (A).

Further, the present inventors also studied a cleaning process for cleaning the inside of the reaction vessel or the inside of the exhaust pipe at each film forming cycle, and this cleaning gas was decomposed with low energy. Chlorine trifluoride (ClF ₃ ) gas has been adopted, which has the merit of being highly reactive and having an extremely fast cleaning rate. The chlorine trifluoride (ClF ₃ ) gas is a gas having a very high corrosiveness. Therefore, depending on the material of the heater used, the discoloration of the external appearance progresses and the inside deteriorates by being eroded and the performance is deteriorated. In some cases, the above-mentioned effects were not obtained.

Accordingly, the present inventors have conducted intensive studies on the material of the heater. For example, heaters of various materials are specifically installed inside the exhaust pipe, and the formation of a functional deposited film and a cleaning process using chlorine trifluoride (ClF ₃ ) gas are repeated several times to improve durability. The test was performed. And it has been found that a heater made of graphite in particular has no deterioration in performance and no change in appearance, etc., and exhibits very good results.

As described above, the present inventors installed a heater made of graphite that is durable against chlorine trifluoride (ClF ₃ ) gas inside the exhaust pipe, and set the inside of the exhaust pipe. Preferably, by forming the deposited film while heating to 200 ° C. or more, the by-product components in the unreacted gas exhausted to the exhaust processing system are turned into a film state or a gas (gas) state by a thermal CVD effect, and the exhaust is performed. The inventors have found that the amount of polysilane deposited inside the pipe can be significantly reduced, and have completed the present invention.

[0042]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an example of a case where a functional deposition film is formed according to the present invention and a cleaning process is performed using a chlorine trifluoride (ClF ₃ ) gas will be described with reference to the drawings. .

FIG. 1 shows a high frequency (hereinafter referred to as "RF") plasma CV having a heating means inside the exhaust pipe of the present invention.
FIG. 3 is a schematic vertical sectional view showing an example of a deposition film forming apparatus by a method D.

This apparatus is roughly classified into a deposition apparatus (19)
1), source gas supply device (192), reaction vessel (10
1) It comprises an exhaust device (193) for reducing the pressure inside.

In the reaction vessel (101), an Al cylindrical substrate (108), a cylindrical substrate holder (105) for holding the Al cylindrical substrate (108), a heating heater (106), A gas introduction pipe (107) is installed, and a high-frequency matching box (117) and a high-frequency power supply (110) are further connected. In addition, the reaction vessel (10
1) also serves as an electrode, and is composed of an upper lid (102), a base plate (103), an insulator (104) and the like.

The raw material gas supply device (192) includes silane (SiH ₄ ), germane (GeH ₄ ), hydrogen (H ₂ ), methane (CH ₄ ), diborane (B ₂ H ₆ ), phosphine (PH ₃ ), and the like. Raw material gas cylinder (131-
136) and a source gas cylinder valve (141) for forming a deposited film.
146), a gas pressure regulator (181 to 186), a source gas inflow valve for deposition film formation (151 to 156), a source gas outflow valve for deposition film formation (161 to 166), and a mass flow controller (171 to 176). ), And each gas cylinder for forming a deposited film is provided with a valve (11).
5) and the reaction vessel (1) via the raw material gas pipe (109).
01) is connected to the gas introduction pipe (107).

The cleaning material gas cylinder (13)
7, 138) and a cleaning material gas cylinder valve (1
47, 148), gas pressure regulators (187, 188),
Cleaning material gas inflow valves (157, 158),
Cleaning material gas outflow valve (167, 168),
And a mass flow controller (177, 178), and a cylinder for each cleaning source gas is connected to a gas introduction pipe (107) disposed in the reaction vessel (101) via a valve (116).

The exhaust device (193) is connected to the reaction vessel (10).
Exhaust piping (11) from 1) to the exhaust pump (194)
1), and a heater (195) made of graphite is installed inside the exhaust pipe (111).

In the present invention, the shape of the heater made of graphite is preferably a shape that covers the entire inside according to the shape of the exhaust pipe. More specifically, a shape that gives a thermal CVD effect without causing exhaust resistance to all unreacted gases that did not become a deposited film exhausted to the exhaust processing system in the process of passing through the exhaust pipe. It is preferred that

Further, a vacuum-sealing seal material is used for the connection part of the exhaust pipe. If the temperature of the connection part of the exhaust pipe becomes too high, the seal material is broken, the sealing effect is impaired, and the vacuum tightness is maintained. It is preferable to cool it because it will be lost. Examples of the cooling means for cooling include an air cooling means using a fan or the like driven by a motor and a water cooling means using a liquid such as water. Any cooling means may be used as long as it has a cooling effect.

The exhaust device (193) includes a leak valve (112), a main valve (113), and a vacuum gauge (1).
14) is also provided.

The formation and cleaning of the deposited film using this apparatus can be performed, for example, as follows.

First, the exhaust pipe (1) is set with the Al-made cylindrical substrate (108) set in the cylindrical-substrate holder (105) for holding the Al-made cylindrical substrate (108).
11) Inside the heater made of graphite (1)
95), and the inside of the exhaust pipe is controlled to a temperature of 200 ° C. or more by the temperature control device (196). And
When the inside of the exhaust pipe reaches a predetermined temperature, the inside of the reaction vessel (101) is exhausted.

Subsequently, the surface temperature of the Al cylindrical substrate (108) was raised to 200 ° C. by the heater (106).
The temperature is controlled to a predetermined temperature of 400 to 400 ° C. When the Al-made cylindrical substrate (108) has reached a predetermined temperature, the source gas cylinder valves for deposition film formation (141 to 146), the source gas inflow valves for deposition film formation (151 to 156), the source material for deposition film formation A necessary one of the gas outflow valves (161 to 166) is opened, and a source gas cylinder (131 to 1) for forming a deposited film is opened.
36), a predetermined gas is introduced into the reaction vessel (101) via the gas introduction pipe (107).

Next, the mass flow controller (171)
176), each raw material gas is adjusted so as to have a predetermined flow rate. At that time, the internal pressure of the reaction vessel (101) was 13
Exhaust device (193) so as to have a predetermined pressure of 3 Pa or less
To adjust.

When the internal pressure becomes stable, the high-frequency power supply (11)
From 0), high-frequency energy is introduced into the reaction vessel (101) through the high-frequency matching box (117) to generate glow discharge. With this discharge energy,
The source gas for forming a deposited film introduced into the reaction vessel (101) is decomposed, and a predetermined functional deposited film is formed on the surface of the Al cylindrical substrate (108).

After removing the Al cylindrical substrate (108) from the reaction vessel (101), an Al cylindrical substrate (not shown) for cleaning is put in place of the Al cylindrical substrate (108). Then, the inside of the reaction vessel (101) is evacuated to a predetermined pressure by the exhaust device (193).

When a predetermined pressure is reached, the valve (116)
And open the gas cylinder for cleaning material (137, 13
8), the reaction vessel (10)
1) A chlorine trifluoride (ClF ₃ ) gas is introduced as a cleaning raw material gas from a gas introduction pipe (107) arranged in the inside. This chlorine trifluoride (ClF ₃ ) gas comes into contact with and reacts with the deposited film or polysilane, whereby the decomposition process proceeds.
A cleaning process is performed on the inside of the reaction vessel (101) and the exhaust pipe (111).

In the present invention, silane (SiH ₄ ), disilane (Si ₃ H ₆ ), silicon tetrafluoride (SiF ₄ ), and disilicon hexafluoride (Si ₂ Source gas for forming amorphous silicon such as F ₆ );
Alternatively, the use of a mixed gas thereof is also effective.

In the present invention, it is also effective to use hydrogen (H ₂ ), argon (Ar), helium (He) or the like as the diluent gas.

As a characteristic improving gas for changing the band gap width of the deposited film, an element containing a nitrogen atom such as nitrogen (N ₂ ) and ammonia (NH ₃ ), oxygen (O ₂ ), nitrogen monoxide ( NO), nitrogen dioxide (NO ₂ ), nitrous oxide (N ₂ O), carbon monoxide (CO), carbon dioxide (CO ₂ )
Elements containing oxygen atoms such as methane (CH ₄ ), ethane (C ₂ H ₆ ), ethylene (C ₂ H ₄ ), acetylene (C
₂ H _2), hydrocarbons such as propane (C ₃ H _8), tetrafluoroboric germanium (GeF _4), fluoride compounds such as nitrogen trifluoride (NF _3), or by a companion these mixed gases Is also effective.

For doping purposes, diborane (B ₂ H ₆ ), boron fluoride (BF ₃ ), phosphine (P
It is also effective to simultaneously introduce a dopant gas such as H ₃ ) into the discharge space.

The type of the deposited film or by-product to be subjected to the cleaning process is not particularly limited. For example, silicon (Si), tungsten (W), boron carbide (BN), transparent conductive film (ITO), chlorine trifluoride, etc. Any substance having a cleaning action by (ClF ₃ ) may be used.

[0064]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

<Reference Example 1> An Al cylindrical substrate (108) having a diameter of 108 mm, a length of 358 mm, and a thickness of 5 mm was mounted on a cylindrical substrate holder (1) using the deposited film forming apparatus shown in FIG.
05), a heater made of tungsten is used as the heater (195) inside the exhaust pipe (111), and the inside of the exhaust pipe (111) is shown in Table 2 by the temperature controller (196). 50 ° C ~ 1 as shown
It heated to 000 degreeC (further, it carried out also when the heater was not installed). When the inside of the exhaust pipe (111) reached a predetermined temperature, a functional deposition film was formed under the conditions shown in Table 1. That is, by the formation of this functional deposited film, an Al base (301) as shown in FIG.
A charge injection blocking layer (302) and a photoconductive layer (30)
3) An electrophotographic photosensitive member was prepared by sequentially laminating the surface layer (304). The electrophotographic photosensitive member was taken out of the cylindrical reaction vessel, and the state of the polysilane and the state of the heater deposited inside the exhaust pipe (111) were evaluated by the evaluation method described later. Table 2 shows the results.

[0066]

[Table 1]

[0067]

[Table 2]

"Amount of polysilane" A comparison was made based on the amount of polysilane present inside the exhaust pipe when no heater was installed inside the exhaust pipe, and evaluated as follows. A: The amount of polysilane was clearly reduced as compared with the case without the heater.・ ・ ・: The amount of polysilane was slightly reduced as compared with the case without the heater. Δ: The level of the polysilane was the same level as in the case without the heater. X: The amount of polysilane was clearly increased as compared with the case without the heater. "State of the heater" The appearance and performance of the heater,
Evaluation was made as follows.・ ・ ・: No change.・ ・ ・: Discoloration is observed in the appearance of the heater, but there is no problem in performance. Δ: The heater is deteriorated by further discoloration of the external appearance, and the required power cannot be obtained because the performance is reduced. ×: Heating cannot be performed because the heater itself melted and disappeared.

As is evident from the results shown in Table 2, by installing a heater inside the exhaust pipe and heating it to 200 ° C. or higher, the amount of polysilane deposited inside the exhaust pipe was reduced.

<Reference Example 2> A functional deposition film was formed by using the deposition film forming apparatus shown in FIG. 1 and heating the exhaust pipe (111) at 200 ° C. in the same manner as in Reference Example 1. Thereafter, the produced electrophotographic photoreceptor is taken out of the reaction container, the cylindrical Al base for cleaning is set at a predetermined position, and chlorine trifluoride (ClF ₃ ) is used as a cleaning raw material.
Using a gas, Ar was used as an inert gas to be introduced simultaneously with the vaporized (gas) state of ClF ₃ , and the cleaning process was performed under the cleaning conditions shown in Table 3. further,
The formation of the functional deposited film and the cleaning process were performed under the same conditions for a total of 20 cycles. The state of the heater installed inside the exhaust pipe (112) after 20 cycles was evaluated by the same evaluation method as in Reference Example 1. Table 4 shows the results. The results for the state immediately after Reference Example 1 (200 ° C.) are also shown in Table 4 for comparison.

[0071]

[Table 3]

[0072]

[Table 4]

As is clear from the results shown in Table 4, in the process of performing 20 cycles of the formation of the functional deposited film and the cleaning process using chlorine trifluoride (ClF ₃ ) having high corrosiveness as the cleaning raw material, tungsten was removed. When a heater made of a material is used, it can be seen that the discoloration of the external appearance is further advanced and the power required for heating cannot be supplied due to deterioration.

<Example 1, Reference Example 3> Except that the material of the heater (195) installed inside the exhaust pipe (112) was changed as shown in Table 5 using the deposited film forming apparatus shown in FIG. In the same manner as in Reference Example 2, a highly corrosive chlorine trifluoride (ClF ₃ )
A cleaning process using gas was performed for 20 cycles, and the state of the heater was evaluated by the same evaluation method as in Reference Example 1. Table 5 shows the results. The results for Reference Example 2 (heater made of tungsten) are also shown in Table 5 for comparison.

[0075]

[Table 5]

As is evident from the results shown in Table 5, the formation of the functional deposited film and the cleaning treatment using highly corrosive chlorine trifluoride (ClF ₃ ) as the cleaning raw material were carried out for 20 days.
Even when the cycle was performed, if graphite was used as the heater material, a very excellent effect was obtained in that the heater state did not change and there was no deterioration.

Example 2 Example 1 (the material of the heater was graphite) except that a functional deposited film shown in Table 6 was formed using the deposited film forming apparatus shown in FIG.
An electrophotographic photoreceptor was produced in the same manner as described above. That is, in the present embodiment, as shown in FIG.
1) An electrophotograph in which a charge injection blocking layer (302), a first photoconductive layer (303-1), a first photoconductive layer (303-2), and a surface layer (304) are sequentially stacked on the charge injection blocking layer (302). A photoreceptor was produced. Then, as in Example 1, this deposited film formation and cleaning treatment using chlorine trifluoride (ClF ₃ ) gas were performed for 20 cycles, and the state of the heater was evaluated by the same evaluation method as in Reference Example 1. Table 7 shows the results. The results for Example 1 are also shown in Table 7 for comparison.
It is described together.

[0078]

[Table 6]

[0079]

[Table 7]

As is clear from the results shown in Table 7, even when functional deposition films having different layer structures were formed, the state of the heater made of graphite did not change, and there was no deterioration. Was.

<Embodiment 3, Comparative Example 1> The interior of the exhaust pipe (111) was heated at 400 ° C. by a heater (195) made of graphite using the deposition film forming apparatus shown in FIG.
, And a functional deposited film was formed under the conditions shown in Table 8. Next, a cleaning process was performed under the conditions shown in Table 9. At that time, the cleaning process time and the amount of chlorine trifluoride (ClF ₃ ) gas used as a cleaning material were determined.
It was evaluated by the evaluation method described below. In Comparative Example 1,
As shown in FIG. 2, a heater was not installed inside the exhaust pipe (211), and the other steps were the same as in Example 3, except that a functional deposition film was formed and a cleaning process was performed. Table 10 shows the results.

[0082]

[Table 8]

[0083]

[Table 9]

[0084]

[Table 10]

[Cleaning time] Evaluation was made based on a relative value when the cleaning time of Comparative Example 1 was 100%. "Amount of Cleaning Material Used" Evaluation was made based on a relative value when the amount of cleaning material used in Comparative Example 1 was 100%.

As is clear from the results shown in Table 10, by heating the inside of the exhaust pipe during the formation of the functional deposition film, the cleaning processing time can be greatly reduced, and the amount of the cleaning material used can be significantly reduced. Was.

Example 4 and Comparative Example 2 Except that the heating temperature inside the exhaust pipe (111) was set to 700 ° C. using the deposited film forming apparatus shown in FIG.
The formation of the functional deposited film and the cleaning process were performed for 20 cycles. Then, the oil of the exhaust pump (194) was changed and the exhaust pump (194) was maintained. The deterioration state of the oil at that time and the state inside the exhaust pump (194) were evaluated by an evaluation method described later. In Comparative Example 2, as shown in FIG. 2, a heater was not installed inside the exhaust pipe (211), and the other steps were the same as in Example 4 except that a functional deposition film was formed and a cleaning process was performed. . Table 11 shows the results.

[0088]

[Table 11]

"Oil Deterioration State" The state of the oil of Comparative Example 2 was visually checked, and the viscosity of the oil was measured with a viscometer, and compared with this, the following evaluation was made. A: The oil is not contaminated and there is no change in viscosity.・ ・ ・: The oil of Comparative Example 5 is not as dirty and the viscosity is not reduced. Δ: No change even when compared to the oil state of Comparative Example 5. ×: Obviously stained and lower in viscosity than the oil of Comparative Example 5. "State inside the exhaust pump" The amount of polysilane inside the exhaust pump of Comparative Example 2 and the state of the rotor inside the pump were visually checked, and compared with the above, the following evaluation was made. ◎ ・ ・ ・ No polysilane is mixed in the exhaust pump, and there is no wear on the rotor inside the pump.・ ・ ・: The amount of polysilane mixed in the exhaust pump is smaller than that of Comparative Example 2, and the rotor inside the pump is less worn. Δ: Compared with Comparative Example 2, the amount of polysilane deposited inside the exhaust pump and the wear of the rotor inside the pump were at the same level. ×: The amount of polysilane deposited inside the exhaust pump is larger than that of Comparative Example 5, and the rotor inside the pump is worn more.

As is clear from the results shown in Table 11, by heating the inside of the exhaust pipe during the formation of the functional deposition film, the amount of polysilane mixed in the exhaust pump can be reduced, and the deterioration of oil can be reduced. did it.

[0091]

As described above, according to the present invention, the by-product components in the unreacted gas which did not become the functional deposition film exhausted to the exhaust treatment system are converted into the film state or gas by the thermal CVD effect. (Gas) state, whereby the amount of polysilane deposited inside the exhaust pipe can be significantly reduced. As a result, the cleaning processing time can be shortened, the amount of cleaning material used can be reduced, the deterioration of the exhaust pump oil can be reduced, and the deterioration of the exhaust pump can be reduced, so that the manufacturing cost can be significantly reduced.

[Brief description of the drawings]

FIG. 1 shows an RF having a heating means inside an exhaust pipe of the present invention.
1 is a schematic vertical sectional view showing an example of a deposited film forming apparatus by a plasma CVD method.

FIG. 2 is a schematic longitudinal sectional view showing an example of a conventional apparatus for manufacturing a deposited film by an RF plasma CVD method.

FIGS. 3A and 3B are schematic cross-sectional views illustrating the layer configuration of an electrophotographic photosensitive member.

[Explanation of symbols]

101, 201 Reaction vessel 102, 202 Top lid 103, 203 Base plate 104, 204 Insulator 105, 205 Cylindrical base holder 106, 206 Heating heater 107, 207 Gas inlet tube 108, 208 Al cylindrical base 109, 209 Source gas Piping 110, 210 High-frequency power supply 111, 211 Exhaust piping 112, 212 Leak valve 113, 213 Main valve 114, 214 Vacuum gauge 115, 215 Valve 116, 216 Valve 117, 217 High-frequency matching box 131-136, 231-236 Deposition film formation Source gas cylinders for use 137-138, 237-238 Cleaning source gas cylinders 141-146, 241-246 Source gas cylinder valves for depositing film formation 147-148, 247-248 Cleani Source gas cylinder valves 151-156, 251-256 Source gas inflow valves for deposition film formation 157-158, 257-258 Cleaning source gas inflow valves 161-166, 261-266 Source gas outflow valves 167-168 for deposition film formation 267-268 Cleaning material gas outflow valves 171-178, 271-278 Mass flow controllers 181-188, 281-288 Gas pressure controllers 191,291 Deposition devices 192,292 Source gas supply devices 193,293 Exhaust devices 194,294 Exhaust pumps 195 Heater 196 Temperature control device 301 Al base 302 Charge injection blocking layer 303 Photoconductive layer 303-1 First photoconductive layer 303-2 Second photoconductive layer 304 Surface layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Katagiri 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Tetsuya Karaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Koji Hitsuishi 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H068 DA23 EA02 EA30 4K030 AA06 AA17 BA29 CA02 CA16 DA06 FA03 KA30 LA17 5F004 AA15 BB29 BC02 BD04 DA00 5F045 AA08 AB04 AC01 AC07 AC19 CA13 DP25 EB06 EG01 EG10 EH15 EK06 5F051 AA05 CA16 CA40

Claims (3)

[Claims] 1. A reaction space comprising a vacuum-tight region, a substrate holder capable of setting a substrate for forming a deposited film in the reaction space, and a source gas for introducing a source gas into the reaction space. Introduction means, heating means for heating the substrate, high-frequency energy introduction means for introducing high-frequency energy into the reaction space to generate glow discharge by excitation of the source gas, and exhausting the reaction space. An apparatus for forming a deposited film by a plasma CVD method having an exhaust pipe, comprising means for introducing chlorine trifluoride (ClF ₃ ) gas;
And a heater made of graphite is installed inside the exhaust pipe. 2. A substrate is placed in a reaction space consisting of a vacuum-tight region, a source gas is introduced into the reaction space, and a high-frequency energy is introduced into the reaction space to cause glow discharge by excitation of the source gas. In a method of forming a deposited film by a plasma CVD method in which a deposited film is generated by generating a deposited film, the inside of the exhaust pipe is heated by a heater made of graphite which is installed inside an exhaust pipe for exhausting the reaction space. A method of forming a deposited film, wherein a deposited film is formed, and a chlorine trifluoride (ClF ₃ ) gas is used for a cleaning process after the deposited film is formed. 3. The heating temperature (A) inside the exhaust pipe is 20.
3. The method according to claim 2, wherein the temperature is controlled within a range of 0.degree. C..ltoreq. (A).