JP2002222800A - Etching method and deposited film forming apparatus with etching function - Google Patents

Abstract

(57) [Problem] To provide a method for reliably and efficiently performing an etching step performed after completion of film formation, and an apparatus suitable for the method. SOLUTION: At least, a raw material gas is introduced into a vacuum reaction vessel for film formation using a substrate and a substrate holding component, and a deposited film is formed by high-frequency discharge. A method and an apparatus for etching a deposited film adhered in a vacuum reaction vessel for film formation and an exhaust pipe with an etching gas during a period from when a vacuum transport container is taken out to when a dummy substrate is charged.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deposited film on a cylinder, especially a functional deposited film, particularly a semiconductor device, an electrophotographic photosensitive member, a line sensor for image input, an imaging device, a photovoltaic element, and the like. The present invention relates to a method and an apparatus for etching a substrate holding component used when forming a light receiving member using a non-single crystalline deposited film such as an amorphous or polycrystalline used.

[0002]

2. Description of the Related Art Conventionally, semiconductor devices, photoreceptor devices for electrophotography, line sensors for image input, imaging devices, photovoltaic devices, and various other electronics.
As an element member used for an element, an optical element, or the like, amorphous silicon, for example, amorphous silicon compensated with hydrogen and / or halogen (eg, fluorine, chlorine, etc.) (hereinafter “a”)
-Si: (H, X) ") and the like, and a deposited film for a semiconductor made of a material has been proposed, and some of them have been put to practical use.

[0003] Such a deposited film is formed by plasma CVD.
That is, a method in which a raw material gas is decomposed by direct current, high frequency, or microwave glow discharge to form a thin film deposition film on a cylinder made of a material such as glass, quartz, heat-resistant synthetic resin, film, stainless steel, or aluminum. Are known. At the same time, an unnecessary deposited film is formed on the base holding component or the auxiliary component.

[0004] For this purpose, various methods and apparatuses have been proposed for removing unnecessary deposited films deposited on the substrate holding component or the auxiliary component.

For example, Japanese Patent Application Laid-Open No. 11-243059 discloses a technique of a semiconductor manufacturing apparatus provided with an etching gas introducing section dedicated to an exhaust pipe in order to remove a by-product adhering to the inside of the exhaust pipe. Have been.

According to JP-A-1-231936, in a method for cleaning a processing apparatus having a processing chamber and a gas supply system connected to the processing chamber, chlorine trifluoride gas is heated in the gas supply system. There is disclosed a method and an apparatus technology for supplying a gas while performing dry etching to clean the inside of the processing chamber.

According to Japanese Patent Application Laid-Open No. 6-196416, after the formation of the deposited film is completed, the holding component of the drum is replaced with a C component.
There has been disclosed a technique of performing an etching process for removing a deposited film adhered by an IF ₃ gas to produce a drum with few image defects.

According to Japanese Patent Application Laid-Open No. 9-222744, the holding component of the drum is replaced
There has been disclosed a technique for improving the drum characteristics by performing plasma cleaning after performing an etching process for removing a deposited film adhered by IF ₃ gas.

[0009] These techniques have improved the uniformity of the film thickness and film quality of the electrophotographic photoreceptor, and accordingly, the yield has been improved to some extent. For example, FIG. 2 is a flow chart of film formation and etching by a deposition film forming apparatus using RF. FIGS. 3, 4 and 5 are schematic sectional views showing an example of a deposited film forming apparatus using RF.

Referring to FIG. 3, the apparatus is roughly classified into a vacuum charging vessel (2010), a vacuum heating vessel (2011), and a vacuum reaction vessel for film formation.
(2012), vacuum cooling vessel (2013), vacuum transfer vessel (2034) and gate (2035). Each container is composed of a vacuum exhaust device (2014 to 2017) for reducing pressure and a gate unit vacuum exhaust device (2018 to 2021).

Referring to FIG. 4, a vacuum reactor (2012) for film formation has a substrate and a substrate holding part (2112), a heater for heating a support (2124), and a ceramic ring (212).
2), a source gas inlet pipe (2107) is installed, and further, outside the film forming vacuum reaction vessel (2012), a gas distribution pipe (2116), a source gas inlet valve (2108), an exhaust pipe (2109) , Exhaust valve (211
8), leak valve (2117), vacuum gauge (2119), power supply & matching box (2115) are connected.

As shown in FIG. 5, the base and the base holding part (2112) are composed of a cap (2120) and a connection ring (213).
0) and an Al cylinder (2123) are installed in a holder (2114). The dummy base (2113) also has the same configuration as the base and the base holding part (2112), and is set on the support heater (2124) in the vacuum reactor for film formation (2012) during etching. .

In forming a deposited film using such a conventional deposited film forming apparatus, a drum is manufactured by performing a predetermined operation. After film formation, the vacuum transfer container is connected, the gate valve is opened, and the substrate and the substrate holding component are taken out of the vacuum reaction container and cooled. After cooling, the cap is removed and the drum and connecting ring are removed.

Next, the base holding parts such as the cap, the connection ring, and the holder are etched by ClF ₃ gas,
Alternatively, wet deposition is performed to remove the deposited film. Auxiliary parts such as a raw material gas introduction pipe and a ceramic ring are installed in a deposition film forming apparatus, and a dummy base is installed on a heater for heating a support, and etching is performed using a ClF ₃ gas. Then, after the etching in the deposition film forming apparatus is completed, A
The film is formed by installing a l cylinder.

With such a deposited film forming apparatus, a drum excellent in apparatus efficiency, production efficiency and running cost is produced.

[0016]

However, the photoreceptor for electrophotography made by the conventional apparatus has been improved in the yield and the uniformity of the film thickness and film quality. In fact, there is still room for further improvement. In particular, it is required to increase the yield and production efficiency.

Under these circumstances, to further increase the yield and the production efficiency, it is necessary to improve the efficiency of the etching method and the apparatus.

For this purpose, after connecting the vacuum transfer container and taking out the base and the base holding parts, the deposited film adhering to the inside of the vacuum reaction container and the exhaust pipe is etched with an etching gas before the dummy base is charged. Do. Thereafter, when the base and the base holding component are installed, the deposited film in the vacuum reaction vessel and the exhaust pipe is peeled off and adheres to the Al cylinder, and the deposited film abnormally grows, and it is necessary to prevent the occurrence of image defects. is there.

It is also necessary to review the etching method to reduce the time and improve the production efficiency. By making these improvements, the cost of the A-Si photoconductor can be reduced.

An object of the present invention is to provide a conventional Cl as described above.
An object of the present invention is to overcome the problems in the etching method using the F ₃ gas and solve the above-mentioned problems in the etching method of an apparatus used for an electrophotographic photosensitive member so as to satisfy the above-mentioned requirements.

That is, a main object of the present invention is to provide an etching method and apparatus for an apparatus capable of desirably sharply reducing image defects and improving production efficiency by efficiently removing a deposited film in a vacuum reaction vessel and an exhaust pipe. Is to provide.

Another object of the present invention is to improve various physical properties of a film to be formed, a film forming speed, reproducibility, improve film productivity, and dramatically improve the yield when mass production is performed. It is an object of the present invention to provide a method and an apparatus for etching an apparatus which enables the above.

[0023]

Means for Solving the Problems The present inventors have developed a conventional C
After overcoming the above-mentioned problems in the etching method using lF ₃ gas and achieving the object of the present invention, the substrate after the film formation and the substrate holding parts were taken out by a vacuum carrier, and then the dummy was removed. By removing the deposited film in the vacuum reaction vessel and the exhaust pipe by etching before the substrate is charged, the occurrence of image defects in the obtained electrophotographic photosensitive member is drastically reduced, and the production efficiency is increased. It turns out.

The present invention has been completed based on the findings. That is, a substrate is installed using a substrate holding component in a reaction space formed in an inner peripheral surface of an electrode constituting at least a part of a side wall of the reaction chamber, and the reaction space is vacuum-tightly sealed to introduce a raw material gas. After applying energy to excite the source gas to generate a glow discharge and form a deposited film on the substrate, the substrate and the substrate holding component are taken out by a vacuum transport container, and the film forming vacuum reaction container is etched. In the method of removing the deposited film adhered to the inside, the etching step includes (1) taking out the base and the base holding component by the vacuum transfer container, and before the dummy base is charged, the etching step (2) a step of etching the deposited film adhered in the vacuum reaction vessel and the exhaust pipe with an etching gas; And a step of etching a deposited film adhered in a vacuum reactor for film formation.

Further, the present invention provides an electrode forming at least a part of a side wall of a reaction chamber, a vacuum-tightly sealed reaction space provided in an inner peripheral surface of the electrode, and a deposition film in the reaction space. A substrate holding component for installing a substrate for formation, a source gas introducing means for introducing a source gas into the reaction space, and a glow discharge by exciting the source gas introduced into the reaction space Etching gas for introducing an etching gas in a deposition film forming apparatus having a high-frequency energy introducing means for introducing high-frequency energy for making use of the cylindrical electrode, and an exhaust means for exhausting the reaction space. Means, a vacuum transfer container which is a means for housing the base and the base holding component and carrying out the reaction space, and a dummy base to be charged in place of the base in the etching step, The etching gas, further comprising: means for etching the deposited film adhered in the film forming vacuum reaction vessel and the exhaust pipe with an etching gas; and etching gas control means for controlling introduction and exhaust of the etching gas. The control unit is configured to at least separately deposit the deposition adhered in the film forming vacuum reaction vessel and the exhaust pipe between the time when the substrate and the substrate holding component are unloaded and the time when the dummy substrate is loaded after the film formation is completed. The present invention relates to a deposited film forming apparatus having an etching function, which has a control system for etching a film with an etching gas.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS By the way, if the etching is performed from the film formation in the flow chart as shown in FIG. 2, as shown in the flow chart, a vacant time occurs in the production apparatus from the completion of the film formation to the start of the etching. There is. In addition, there is no opportunity to etch the deposited film attached to the support heater 2124.

Among them, the cause of the defect is not exactly known, but is presumed to be roughly as follows. In the case of the flow as shown in FIG. 2, depending on the apparatus configuration and film forming conditions, after forming the film, a vacuum transfer container is connected, and after taking out the base and the base holding parts, a dummy base is set and the inside of the vacuum reaction container is set. Even if the deposited film is etched, a slight deposited film on the support heater inside the dummy substrate is not removed. This piece of the deposited film may peel off when the dummy substrate is taken out, drift in the vacuum vessel, adhere to the Al cylinder when the substrate and the substrate holding part are installed, and cause a defect of the electrophotographic photosensitive member.

[0028] Further, the cause of the idle time in the production apparatus is that it takes time to adjust the pressure in the vacuum reaction container for film formation and the inside of the vacuum transfer container, and to relieve the atmosphere when the vacuum transfer container takes a dummy substrate. It is.

The problems of these defects of the deposited film and the problem of the idle time of the production equipment are as follows. The flow shown in FIG.
It can be solved by removing it. In addition, by performing this etching, the etching time after the dummy substrate is put in becomes shorter than before.

In the present invention, the etching gas is Cl
By using F ₃ gas, the etching speed becomes faster and the post-processing becomes easier.

Further, by performing a slight heating at the time of etching just before the dummy substrate is put, the etching speed is increased.

The inert gas introduced simultaneously with the ClF ₃ (chlorine trifluoride) gas used in the present invention includes:
He, Ne, and Ar are preferred.

The concentration of ClF ₃ , ie, [ClF ₃ /
If the value of (ClF ₃ + inert gas)] × 100% is too small, not only the etching effect is weakened, but also the etching tact is extended. Conversely, if the concentration is too high, the reaction will be abrupt and fine powder will increase. In addition, since the load on the pump increases, practically, 10% or more and 70% or less are suitable for the present invention.

In the present invention, the etching with the etching gas before the introduction of the dummy substrate is performed by introducing a mixed gas of ClF ₃ and an inert gas into the vacuum reactor for film formation and sealing the introduced gas in the reactor. It is effective in any case where the plasma is formed by applying high frequency power while introducing a gas.However, the latter is practically used because the reaction speed is increased and the tact is shortened. Is more suitable.

In the present invention, immediately before the dummy substrate is put in, the etching gas is once completely drawn off,
It is possible to prevent the etching gas from flowing into the vacuum carrier. In addition, in the etching after the introduction of the dummy substrate, the deposited film can be more easily removed by applying a high-frequency discharge. In addition, by performing a surface treatment such as thermal spraying on the surface of the support heater, the heater surface can be protected by the etching gas.

In the present invention, the etching gas pipe is
It may be provided anywhere in the exhaust pipe from the reaction vessel outlet to the exhaust device inlet. Then, the etching speed is further improved by introducing the etching gas into both the gas introduction pipe and the gas introduction pipe in the vacuum reactor for film formation.

By satisfying the above range, it becomes possible to remove the deposited film in the vacuum reaction vessel and the exhaust pipe, and the film fragments of the deposited film floating in the vacuum reaction vessel at the time of loading the substrate and the component holding the substrate. It becomes difficult to adhere to the surface of the Al cylinder. As a result, the yield of the electrophotographic photoreceptor obtained is reduced due to the reduced number of defects, and the etching time after the introduction of the dummy base is shortened as compared with the conventional case, thereby increasing the production efficiency.

The above-mentioned effects have been found as a result of studies through experiments by the present inventors.

Hereinafter, the present invention will be described with reference to flowcharts and drawings.

FIG. 1 shows a dummy substrate 2 according to an example of the present invention.
It is a flowchart about the etching before throwing in 113.

The apparatus used by using this flow is the conventional deposited film forming apparatus using the RF system shown in FIGS.

FIG. 6 shows an etching gas introduction pipe 3126 and an introduction valve 312 connected to an exhaust pipe as an example of the present invention.
FIG.

(Substrate: Cylinder) The cylinder used in the present invention may be either conductive or electrically insulating. Al, Cr, M as the conductive cylinder
Metals such as o, Au, In, Nb, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. In addition, a film or sheet of a synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, etc., at least the surface of the electrically insulating cylinder such as glass, ceramic, etc., on the side on which the light receiving layer is formed is formed. Conductive treated cylinders can also be used.

The shape of the cylinder used in the present invention may be a cylindrical or plate-shaped endless belt having a smooth surface or an uneven surface, and the thickness thereof may form a desired electrophotographic photosensitive member. Is determined as appropriate, but when flexibility as an electrophotographic photoreceptor is required,
The thickness can be made as thin as possible within a range where the function as a cylinder can be sufficiently exhibited. However, the size of the cylinder is usually 10 μm or more in terms of production, handling, mechanical strength, and the like.

(Conditions for Forming Deposited Film) In order to form a deposited film by the glow discharge method using the apparatus of the present invention, a source gas for supplying Si atoms, which can supply silicon atoms (Si), is basically used. And a source gas for H supply capable of supplying hydrogen atoms (H) or / and a source gas for X supply capable of supplying halogen atoms (X) are introduced into the reaction vessel in a desired gas state,
A glow discharge is generated in the reaction vessel, and a-Si:
What is necessary is just to form the layer which consists of H and X.

Substances that can serve as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ ,
Silicon hydrides (silanes) in a gas state such as Si ₄ H ₁₀ or capable of being gasified can be used effectively.
Further, SiH ₄ and Si ₂ H ₆ are preferred in terms of ease of handling at the time of forming the layer and good Si supply efficiency.

Then, hydrogen atoms are structurally introduced into the deposited film to be formed, so that the control of the introduction ratio of hydrogen atoms is further facilitated, and in order to obtain film characteristics which achieve the object of the present invention. It is necessary to form a layer by mixing a desired amount of a gas of a silicon compound containing H ₂ and / or He or a hydrogen atom with these gases. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

The source gas for supplying halogen atoms used in the present invention is, for example, a gaseous or gaseous gas such as a halogen gas, a halide, an interhalogen compound containing halogen, or a silane derivative substituted with halogen. The obtained halogen compounds are preferred. 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. In the present invention, halogen compounds that can be suitably used include, specifically, fluorine gas (F ₂ ), BrF,
Inter-halogen compounds such as ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ and IF ₇ can be mentioned. Specific examples of the silicon compound containing a halogen atom, ie, a silane derivative substituted with a halogen atom, include, for example, SiF ₄ , Si ₂
Silicon fluorides such as F ₆ can be mentioned as being preferred.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the deposited film, for example, the temperature of a cylinder, a reaction vessel of a raw material used to contain hydrogen atoms and / or halogen atoms, What is necessary is just to control the amount introduced into the inside, the discharge power, and the like.

In the present invention, it is preferable that the deposited film contains atoms for controlling conductivity as necessary.
The atoms for controlling the conductivity may be contained in the deposited film in a state of being distributed uniformly and evenly, or there may be a part contained in the layer thickness direction in a non-uniform distribution state.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors.
An atom belonging to Group 13 of the periodic table that gives p-type conduction properties, hereinafter abbreviated as `` Group 13 atom '') or an atom belonging to Group 15 of the periodic table, which gives n-type conduction properties (hereinafter `` Group 15 atom '') Can be used.

As the Group 13 atom, specifically, boron
(B), aluminum (Al), gallium (Ga), indium
(In), thallium (Tl) and the like, and B, Al, and Ga are particularly preferable. Specific examples of Group 15 atoms include phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and the like.
Particularly, P and As are preferable.

The content of atoms for controlling conductivity contained in the deposited film is preferably 1 × 10 ^-2 to 1 × 10 ⁴ atoms p
pm, more preferably 5 × 10 ^{−2 to} 5 × 10 ³ atom ppm, and most preferably 1 × 10 ⁻¹ to 1 × 10 ³ atom ppm.

In order to structurally introduce an atom for controlling conductivity, for example, a group 13 atom or a group 15 atom, a material for introducing a group 13 atom or a group 13 atom must be used during layer formation. The source material for introduction may be introduced in a gaseous state into the reaction vessel together with another gas for forming a deposited film. As a raw material for introducing a Group 13 atom or a raw material for introducing a Group 13 atom, a gaseous material at normal temperature and normal pressure or a material which can be easily gasified at least under layer forming conditions is employed. It is desirable.

As such a raw material for introducing a group 13 atom, specifically, for introducing a boron atom, B ₂ H ₆ , B
_{4 H 10, B 5 H 9} , B 5 H 11, B 6 H 10, B 6 H 12, B 6 H 14
And borohydrides such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ , GaCl ₃ , G
a (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like can also be mentioned.
Among them, B ₂ H ₆ is one of the preferable raw materials in terms of handling.

As a raw material for introducing a group 15 atom, phosphorus hydrides such as PH ₃ , PF ₃ , PF ₅ , PCl ₃ , PCl ₅ , and PBr ₃ are effectively used for introducing a phosphorus atom. , PI ₃
And PH ₄ I and the like. In addition, AsH ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , S
bH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , B
iCl ₃ , BiBr _{3 and the} like are mentioned as effective starting materials for introducing Group 15 atoms.

These raw materials for introducing atoms for controlling conductivity may be diluted with H ₂ and / or He, if necessary.

In order to achieve the object of the present invention and to form a deposited film having desired film characteristics, the mixing ratio of the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power and the cylinder temperature Must be set appropriately.

[0059] The flow rate of H ₂ and / or He used as a dilution gas is properly selected within an optimum range in accordance with the layer design, to Si-feeding gas H ₂ and / or He
Is usually controlled in the range of 1 to 20 times, preferably 3 to 15 times, and most preferably 5 to 10 times.

Similarly, an optimum range of the gas pressure in the reaction vessel is appropriately selected according to the layer design.
^{-2 to} 1000 Pa, preferably 5 × 10 ^{-2 to} 500 Pa, and most preferably 1 × 10 ^{-1 to} 150 Pa.

Similarly, the optimum range of the discharge power is appropriately selected according to the layer design. The ratio [W · min / mL (normal)] of the discharge power to the flow rate of the gas for supplying Si is usually 0.1%. ~ 7, preferably 0.5-6, optimally 0.7
It is desirable to set it in the range of -5.

The optimum temperature of the cylinder is appropriately selected according to the layer design.
Desirably, it is set to 350 ° C.

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

[0064]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 Using the deposited film forming apparatus shown in FIGS.
An electrophotographic photoreceptor was manufactured under the following film forming conditions. After the film formation, the vacuum transfer container was connected, the gate valve was opened, the substrate and the substrate holding component were taken out, and the gate valve was closed. Next, ClF _{3 as} an etching gas and Ar as a diluent gas were supplied from a film-forming gas introduction pipe under the conditions shown in Table 2, and etching was started. The vacuum transporter transports the substrate to a predetermined place,
Next, the dummy substrate is transported. After this, ClF ₃ and A
The supply of r was stopped to stop the etching. It took about 10 minutes from the start of etching to the stop, that is, the time from when the vacuum transfer container took out the substrate and transferred the dummy substrate. ClF ₃ and Ar were completely removed. Next, a vacuum carrier was connected, the gate valve was opened, a dummy substrate was loaded, ClF ₃ and Ar were supplied according to the conditions shown in Table 3, and etching was performed while applying a high frequency.

The electrophotographic photosensitive member thus formed was evaluated by the following method.

[Evaluation Method] “Appearance”: The formed electrophotographic photosensitive member was visually observed and evaluated according to the following three grades. ◎ ・ ・ ・ “Especially good”, that is, almost no defects ○ ・ ・ ・ “Good” △ ・ ・ ・ “No problem in practical use” “Cost” ・ ・ ・ Appearance ○ The evaluation was performed in the following three stages. ◎ ・ ・ ・ The ratio between conventional tact and tact is 0.9 or less ○ ・ ・ ・ The ratio between conventional tact and tact is 0.9 or more and 0.95 or less △ ・ ・ ・ The ratio between conventional tact and tact is 0.95 or more and 1.0 or less Consists of two steps. The first step is etching of only the gas after removing the substrate on which the film is formed and before installing the dummy substrate, and the second step is etching by applying high-frequency discharge to the etching gas after installing the dummy substrate. It is.

Further, the conventional tact is a sum of the free time of 10 minutes in the state where the etching of the first step is not performed and the etching time of the second step under the conditions shown in Table 3.

Table 4 shows the results.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

[Table 4]

As is clear from Table 4, since the etching was performed for 10 minutes without the base holding component, the portion which was difficult to be etched conventionally becomes easy to be etched, so that the time of the second step can be shortened. It was also found that the cost was good.

Example 2 As shown in FIG. 3, a gas pipe dedicated to etching was connected to an exhaust pipe of a vacuum reactor for film formation, and a ClF ₃ gas and an Ar gas were introduced. Film formation and etching were performed.

The electrophotographic photosensitive member thus formed was evaluated in the same manner as in Example 1.

[0076]

[Table 5]

As is clear from Table 5, since the etching was performed for 10 minutes without the base holding component, the portion which was difficult to be etched conventionally becomes easy to be etched, so that the time of the second step can be shortened. It was also found that the cost was good.

Example 3 Example 1 was the same as Example 1 except that the etching gas was sealed by closing the exhaust valve during the etching using the deposited film forming apparatus shown in FIGS. The same film formation and etching were performed.

The electrophotographic photosensitive member thus formed was evaluated in the same manner as in Example 1.

[0080]

[Table 6]

As is clear from Table 6, since the etching was performed for 10 minutes without the base holding component, the portion which was difficult to be etched conventionally becomes easy to be etched, so that the time of the second step can be shortened. It was also found that the cost was good.

Example 4 As shown in FIG. 3, a gas pipe dedicated to etching was connected to an exhaust pipe of a vacuum reactor for film formation, and a ClF ₃ gas and an Ar gas were introduced. Film formation and etching were performed.

The electrophotographic photoreceptor thus formed was evaluated in the same manner as in Example 1.

[0084]

[Table 7]

As is clear from Table 7, since the etching was performed for 10 minutes without the base holding parts, the portion which was difficult to be etched conventionally becomes easy to be etched, so that the time of the second step can be shortened. It was also found that the cost was good.

[0086]

According to the present invention, after the completion of the film formation, the etching of the deposited film adhered to the inside of the vacuum reaction vessel for film formation and the inside of the exhaust pipe is carried out from the time when the substrate and the substrate holding parts are taken out by the vacuum transfer container to the time when the dummy substrate is introduced. By doing so, contamination in the film forming apparatus due to peeling of the film from the support heater generated when the dummy substrate is charged into the film forming vacuum reaction vessel was prevented, and the yield was increased.

Further, the etching time after the introduction of the dummy substrate was shortened, and the production efficiency was improved.

[Brief description of the drawings]

FIG. 1 is a flow chart of an etching method for an apparatus of the present invention.

FIG. 2 is a flowchart of an etching method of a conventional apparatus.

FIG. 3 is an overall view of a conventionally used device.

FIG. 4 is a detailed view of a vacuum reactor for film formation for forming a photoreceptor layer of an electrophotographic photoreceptor by an RF method which has been conventionally used.

FIG. 5 is a detailed view of a vacuum reaction vessel for film formation for forming a photoreceptive layer of a conventionally used electrophotographic photoreceptor by an RF method.

FIG. 6 is a schematic view showing an example of the present invention, in which an introduction pipe and an introduction valve dedicated to etching are connected to an exhaust pipe of a vacuum reaction vessel for film formation for forming a photoreceptor layer of an electrophotographic photosensitive member by an RF method. It is sectional drawing.

[Explanation of symbols]

 2010 ・ ・ ・ Vacuum charging vessel 2011 ・ ・ ・ Vacuum heating vessel 2012、3012 ・ ・ ・ ・ ・ ・ ・ Vacuum reactor for film formation 2013 ・ ・・ ・ ・ ・ ・ ・ ・ Vacuum cooling vessel 2014, 2015, 2016, 2017 2027, 2028, 2029Vacuum valve 2030, 2031, 2032, 2033Vacuum valve 2034Vacuum transfer container 2035Gate 2107 3107 ・ ・ ・ ・ ・ ・ ・ ・ Material gas introduction pipe 2108、3108 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Material gas introduction valve 2109、3109 ..Base and base holder 2113 Dummy base 2114 Holder 2115, 3115 Power supply, matching box 2116 , 3116・ ・ ・ ・ ・ ・ Gas distribution pipe 2117、3117 ・ ・ ・ ・ ・ ・ ・ ・ ・ Leak valve 2118、3118 ・ ・ ・ ・ ・ ・ ・ Main exhaust valve 2119、3119 ・ ・ ・ ・ ・ ・ ・ ・ ・ Vacuum gauge 2120 ... Cap 2122, 3122 ... Ceramic ring 2123 ... Al cylinder 2124, 3124 ...・ Heater for heating the support 2130 ・ ・ ・ Connection ring 3125 ・ ・ ・ Introduction valve 3126 ・ ・ ・ Introduction of etching gas tube

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshiyuki Ehara 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Hironori Owaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Masaya Kawada 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) 4K030 AA04 AA06 AA17 BA29 DA06 FA01 KA05 LA17 5F004 AA14 AA15 BD04 CA02 CA03 DA00 DA23 DB02 5F045 AA08 AB04 AC16 BB08 BB14 CA16 DA65 EB06 EH15

Claims (10)

[Claims] 1. A substrate is placed in a reaction space formed in an inner peripheral surface of an electrode constituting at least a part of a side wall of a reaction chamber by using a substrate holding component, and the reaction space is vacuum-tightly sealed and a raw material gas is introduced. After applying a high-frequency energy to excite the source gas to generate a glow discharge and form a deposited film on the substrate, the substrate and the substrate holding component are taken out by a vacuum carrying container, and the film is formed by etching. In the method for removing a deposited film adhered in a vacuum reaction vessel, the etching step includes: (1) after taking out the base and the base holding component by the vacuum transfer container, and before loading a dummy base, A step of etching the deposited film adhering to the inside of the vacuum reactor for film formation and the inside of the exhaust pipe with an etching gas; Wherein the step of etching the deposited film deposited on the film forming vacuum reaction vessel, and carrying out in two steps, the etching method for removing the deposited film. 2. The method according to claim 1, wherein the etching gas is a ClF ₃ gas. 3. The method for etching a deposited film according to claim 1, wherein the etching gas is supplied while exhausting the gas or supplying the gas in a sealed state. 4. The deposited film according to claim 1, wherein the etching gas is exhausted after the completion of the etching step (1) and before the dummy substrate is charged by a vacuum carrier. Etching method. 5. The method for etching a deposited film according to claim 1, wherein said etching step (2) is performed by introducing a high frequency in addition to said etching gas. 6. An electrode constituting at least a part of a side wall of a reaction chamber, a vacuum-tightly sealed reaction space provided in an inner peripheral surface of the electrode, and a substrate for forming a deposited film in the reaction space. A base holding component for installing a source gas; a source gas introducing means for introducing a source gas into the reaction space; and a high frequency for generating a glow discharge by exciting the source gas introduced into the reaction space. An apparatus for forming a deposited film comprising: a high-frequency energy introducing unit that introduces energy using the cylindrical electrode; an exhaust unit that exhausts the reaction space; an etching gas introducing unit that introduces an etching gas; A vacuum transfer container which is a means for storing the substrate and the substrate holding component and carrying the substrate out of the reaction space; a dummy substrate inserted in place of the substrate in the etching step; A means for etching the deposited film adhered to the inside of the vacuum reaction vessel and the inside of the exhaust pipe with an etching gas; and an etching gas control means for controlling the introduction and exhaust of the etching gas. At least after the completion of film formation, between the time when the substrate and the substrate holding component are unloaded and the time when the dummy substrate is loaded, the deposited film adhered to the inside of the film forming vacuum reaction vessel and the exhaust pipe is etched gas. A deposition film forming apparatus with an etching function, characterized by having a control system for performing etching at a time. 7. The method according to claim 7, wherein said etching gas introducing means comprises ClF _3.
7. The deposited film forming apparatus with an etching function according to claim 6, which is a gas introducing means. 8. The deposition film forming apparatus with an etching function according to claim 6, further comprising a means for supplying the etching gas while exhausting the gas, or supplying the gas in a sealed state. 9. The etching function according to claim 6, wherein the means for controlling the introduction and exhaust of the etching gas controls the drawing of the etching gas before the dummy substrate is charged by the vacuum carrier. With deposited film forming equipment. 10. The deposition film forming apparatus with an etching function according to claim 6, further comprising control means for introducing a high frequency in addition to the etching gas and performing a second step of etching after the dummy substrate is charged. .