JP2010205854A - Method of manufacturing semiconductor device - Google Patents

Abstract

Particle generation caused by peeling of deposits on an inner wall surface of a processing container during plasma film formation is suppressed.
A step (A) of forming a first coating film 31 made of a silicon oxide film on the inner wall surface of a processing vessel in which an aluminum fluoride layer 11F is formed on the inner wall surface 11 made of aluminum or an aluminum alloy; After the step (A), the step (B) of forming the second coating film 32 made of a film having a hardness higher than that of the silicon oxide film on the first coating film, and the step (B), A step (C) of carrying a substrate to be processed into a processing container and placing it on a susceptor; and after step (C), a processing gas is introduced into the processing container and a gas phase is applied to the substrate to be processed on the susceptor. A step (D) of forming an insulating film by a growth method, and after the step (D), a gas containing fluorine is introduced into the processing vessel, and the first coating film and the second coating film are formed. D Performing a cleaning step of quenching removed.
[Selection] Figure 3C

Description

  The present invention relates to the manufacture of semiconductor devices, and more particularly to a method of manufacturing a semiconductor device including a film forming process by vapor deposition.

  In manufacturing a semiconductor device, various insulating films are formed on a semiconductor substrate such as a silicon wafer. In particular, a vapor phase growth method for depositing a desired insulating film on a semiconductor substrate using a vapor phase raw material is one of the basic techniques in the manufacture of today's semiconductor devices. Such a vapor phase growth method includes a CVD (chemical vapor deposition) method, a plasma CVD method, and an ALD (atomic layer deposition) method.

  In such a vapor phase growth method, a substrate to be processed such as a silicon wafer is placed on a susceptor provided in a processing container of a film forming apparatus where film deposition is performed, and the processing is performed in a state heated to a predetermined temperature. A gas is introduced into the processing container from, for example, a shower head, the processing gas is decomposed in the vicinity of the surface of the substrate to be processed, and a desired film is deposited on the surface of the substrate to be processed.

  On the other hand, when the processing gas is decomposed, it is avoided that deposits resulting from the decomposition of the source gas are deposited on the inner wall surface of the processing vessel or the surface of the shower head simultaneously with the deposition of a desired film. I can't. For this reason, in the film forming apparatus used in the CVD method, the plasma CVD method, or the ALD method, the deposit deposited on the inner wall surface of the processing vessel or the surface of the shower head is periodically or as required. Removal is performed by a cleaning process.

  Such a cleaning process is generally performed by introducing an etching gas containing fluorine (F) into the processing container. Since the processing container is generally made of aluminum (Al) or an Al alloy, When such a cleaning process is repeated, an aluminum fluoride (AlF) layer is formed on the inner wall surface of the processing container.

JP 2007-180340 A

  By the way, the deposit deposited on the AlF modified layer covering the inner wall surface of the processing vessel formed in this way is easily peeled off, and becomes a particle in the manufacturing process of the semiconductor device, which causes a decrease in yield. Particularly in the ultra-miniaturized semiconductor device having a gate length of, for example, 90 nm or 65 nm or less after the recent 0.1 μm generation, the particle size of particles to be managed has decreased. The generation of particles due to the separation of precipitates is a serious factor that reduces the yield of semiconductor devices. Such an AlF modified layer formed on the inner wall surface of the processing vessel is stable and its removal is not easy.

  In order to suppress the formation of the AlF modified layer on the inner wall surface of the processing vessel, a technique has been proposed in which a remote plasma process is used during the cleaning process and cleaning is performed at a low temperature with low energy fluorine radicals. Even if such a remote plasma process is used, it is difficult to completely suppress the formation of the AlF modified layer because the cleaning process is repeated many times, and it is assumed that the AlF modified layer is formed. Another solution is sought.

  On the other hand, the conventional plasma processing apparatus has a problem that the substrate to be processed is contaminated by a metal element sputtered by plasma from the inner wall surface of the processing vessel. In order to suppress this problem of contamination, conventionally, a technique of covering the inner wall surface of the processing container with a thin silicon oxide film has been used (pre-coating). However, pre-coating with a silicon oxide film is chemically stable, but thin and fragile. In the case of plasma processing such as plasma CVD processing, it may be sputtered by ions or electrons accelerated by an electric field and disappear. There is. When the precoat film disappears, there arises a problem of metal contamination due to sputtering from the exposed AlF film, peeling of deposits deposited thereon, and generation of particles.

  According to one characteristic, a semiconductor device manufacturing method includes: (A) a first made of a silicon oxide film on the inner wall surface of a processing vessel made of aluminum or an aluminum alloy and having an aluminum fluoride layer formed on the inner wall surface. A step of forming a coating film, and a step of forming a second coating film made of a film having a hardness higher than that of the silicon oxide film on the first coating film after the step (A), and (C ) After the step (B), the step of loading the substrate to be processed into the processing container and placing it on the susceptor; and (D) introducing the processing gas into the processing container after the step (C). And an insulating film is formed on the surface of the substrate to be processed placed on the susceptor by vapor deposition, and (E) after the step (D), Etching gas containing fluorine Type, and performing a cleaning step of removing the first coating film and the second coating film by etching.

  By forming the first coating film made of a silicon oxide film on the inner wall surface of the processing vessel on which the aluminum fluoride layer is formed, excellent adhesion between the inner wall surface and the first coating film can be obtained. Even if plasma processing or the like is performed in the processing container, it is possible to effectively suppress the problem of metal contamination on the substrate to be processed and the problem of particle generation due to the peeling of the deposit. In addition, since an aluminum fluoride layer may be formed on the base of the first coating film, the first coating film may be formed by cleaning with an etching gas containing F as needed or with a new coating. Each time the processing substrate is processed, it can be removed on-site in the production line of the semiconductor device, and the internal state of the processing container can be initialized without greatly reducing the manufacturing throughput of the semiconductor device. As a result, the manufacturing yield can be improved particularly in the manufacture of an ultrahigh-speed semiconductor device having a gate length of 100 nm or less.

  Further, by covering the first coating film made of a silicon oxide film with a second coating film having a higher hardness, the sputtering of the first coating film due to high-speed charged particles generated during plasma processing is suppressed. Therefore, the problem of metal contamination of the substrate to be processed and the problem of particle generation can be more effectively suppressed. At that time, the use of a silicon oxide film having excellent adhesion to aluminum or an aluminum alloy as the first coating film improves the adhesion of the second coating film to the inner wall of the processing vessel. To do.

It is a figure which shows the structure of the plasma CVD apparatus used by 1st Embodiment. FIG. 2 is a view (No. 1) showing a state of an inner wall surface of the processing vessel of the plasma CVD apparatus of FIG. FIG. 3 is a diagram (No. 2) illustrating a state of the inner wall surface of the processing container of the plasma CVD apparatus in FIG. 1. FIG. 3 is a diagram (No. 3) illustrating a state of the inner wall surface of the processing container of the plasma CVD apparatus in FIG. 1. It is FIG. (1) which shows 1st Embodiment. It is a figure (the 2) which shows 1st Embodiment. It is FIG. (3) which shows 1st Embodiment. It is a flowchart which shows 1st Embodiment. It is a figure which shows the state of the processing container inner wall surface in the one step of FIG. It is a figure which shows the state of the processing container inner wall surface in the one step of FIG. It is a figure which shows the effect of invention. It is a flowchart explaining the experiment A in FIG. It is a flowchart explaining the experiment B in FIG. It is a flowchart explaining the experiment C in FIG. It is a flowchart which shows 2nd Embodiment.

[First Embodiment]
FIG. 1 shows a configuration of a parallel plate type plasma CVD apparatus 10 used in an embodiment of the present invention. However, the present invention is not limited to the parallel plate type plasma CVD apparatus.

  Referring to FIG. 1, a plasma CVD apparatus 10 includes a processing container 11 that is exhausted from an exhaust port 11A. In the processing container 11, a susceptor 12 that holds a substrate to be processed W, and a target to be processed on the susceptor. A shower head 13 facing the substrate W is provided. In the illustrated example, process gases A to C are supplied to the shower head along with the rare gas in the line 13R via the respective lines 13A to 13C, and discharged toward the substrate W to be processed in the process vessel 11. Is done. Further, the plasma CVD apparatus 10 in FIG. 1 has a line 13D for supplying an etching gas containing F to the shower head 13 as a cleaning gas in a cleaning process. The cleaning gas supplied to the shower head 13 cleans the inside of the shower head 13 and is discharged into the processing space 11B inside the processing container 11 to clean the inside of the processing container 11.

  Further, the shower head 13 and the susceptor 12 are supplied with high-frequency power from a high-frequency power source 14, and the plasma 11P is formed by exciting the rare gas on the surface of the substrate W to be processed. As a result, the processing gas introduced through the lines 13A to 13C is decomposed by the plasma 11P, and a desired film is deposited on the surface of the substrate W to be processed.

  Further, in the configuration of FIG. 1, a gate valve 13 </ b> G is formed to carry in and carry out a part of the substrate to be processed in the processing container 11.

  2A to 2C are enlarged views showing the inner wall surface of the processing container 11 when a film is formed on the substrate W to be processed using the plasma CVD apparatus 10 shown in FIG.

  Referring to FIG. 2A, the inner wall surface 11W of the processing vessel 11 made of Al or an Al alloy is formed with irregularities to prevent deposits from peeling off and becoming particles, but the substrate to be processed As a result of depositing, for example, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film on the W surface, deposits similar to those deposited on the substrate to be processed W are also deposited on the surface of the inner wall 11W. 21 is deposited.

So when the said film on the target substrate W deposition is completed, containing F (fluorine) in the processing vessel 11, for example, it is introduced etching gas such as NF ₃ or CF _4, as shown in FIG. 2B Further, the deposit 21 is removed by cleaning with the etching gas, and the inside of the processing container 11 is initialized. Similar deposition and cleaning are performed on the surface of the shower head 13 and the susceptor 12.

  By the way, as described above, the processing vessel 11 is generally made of Al or an Al alloy. Therefore, when the cleaning is repeated and the inner wall surface 11W of the processing vessel comes into contact with the etching gas containing such F. As shown in FIG. 3A, it is inevitable that the modified layer 11F made of aluminum fluoride (AlF) is formed on the inner wall surface 11W.

  When the film formation as shown in FIG. 2B is performed using the processing container 11 in which the modified layer 11F is formed on the surface of the inner wall surface 11W, the deposit 21 is directly deposited on the modified layer 11F. However, such a deposit 21 is generally low in adhesion to the modified layer 11F made of AlF, so that it is likely to be peeled off and likely to become particles. Further, when a plasma process is performed in the processing vessel, the AlF modified layer is sputtered by accelerated electrons and ions in the plasma, causing a problem of metal contamination of the substrate to be processed.

  Therefore, in the first embodiment of the present invention, as shown in FIG. 3B, prior to the formation of the desired insulating film, the AlF modified layer 11F on the surface of the inner wall surface 11W is covered and made of a silicon oxide film. The first coating film 31 is formed to a thickness of 100 nm to 300 nm, and further, the second coating having a higher hardness such as a silicon carbide (SiC) film covering the first coating film 31 thereon. The film 32 is formed to a thickness of 100 nm to 300 nm.

For example, in the first coating film, the temperature of the susceptor 12 is set to about 400 ° C., and silane (SiH ₄ ) gas, nitrous oxide (N ₂ O) gas, and nitrogen (N ₂ ) gas are respectively supplied to the lines 13A to 13A. The shower head 13 enters the processing space 11B in the processing vessel 11 together with a rare gas such as argon (Ar) gas, helium (He) gas, or krypton (Kr) gas supplied from 13C through the line 13R. The rare gas is introduced at a total pressure of 200 Pa to 650 Pa, for example, and excited by the high frequency power source 14 at a high frequency of 400 kHz, for example. In this state, the inner wall surface 11W of the processing vessel 11 on which the first coating film 31 is formed is generally heated to a temperature of about 100 ° C. to 160 ° C.

The second coating layer is set similarly about 400 ° C. The temperature of the susceptor 12, tetramethylsilane Si (CH _{3) 4} gas, a carbon dioxide (CO ₂₎ gas and nitrogen (N ₂₎ gas Along with the rare gas such as argon (Ar) gas, helium (He) gas, or krypton (Kr) gas supplied from the lines 13A to 13C via the line 13R, the processing space 11B in the processing vessel 11 is filled with It is formed by introducing the total pressure of, for example, 200 Pa to 600 Pa through the shower head 13 and exciting the rare gas with the high frequency power source 14 at a high frequency of, for example, 400 kHz. Even in this state, the inner wall surface 11W of the processing vessel 11 on which the first coating film 31 is formed is generally cooled to a temperature of about 100 ° C. to 160 ° C.

  The first coating film 31 and the second coating film 32 are preferably formed continuously in the processing container 11 without releasing the processing container 11 to the atmosphere. The first coating film thus formed has a refractive index of about 1.46, and the second coating film thus formed has a refractive index of 1.8 to 1.9. Show.

  Similar coating films 31 and 32 are also formed on the surface of the shower head 13 or the susceptor 12.

  The formation of the coating films 31 and 32 in FIGS. 3B and 3C is performed in a state where a wafer is not placed on the susceptor 12, but may be performed in a state where a dummy wafer is placed on the susceptor 12.

  FIG. 4 is a flowchart showing the method for manufacturing the semiconductor device according to the first embodiment, including the steps of forming the coating films 31 and 32.

Referring to FIG. 4, the first coating film 31 and the second coating film 32 are formed on the inner wall surface 11W of the processing container 11 as described with reference to FIG. 3C. A substrate W to be processed is introduced into the container 11 by opening the gate valve 13G and placed on the susceptor 12. After the substrate to be processed W is placed on the susceptor 12, the gate valve 13G is closed.

  Next, in step 2, the susceptor 12 is heated to a predetermined temperature, for example, 400 ° C., a predetermined processing gas is introduced into the processing container 11, and a desired insulating film is formed on the surface of the substrate W to be processed. To do.

For example, when the desired insulating film is a silicon carbide film (SiC film), tetramethylsilane gas is introduced into the line 13A, carbon dioxide gas is introduced into the line 13B, nitrogen gas is introduced into the line 13C, and the line 13R. The desired silicon carbide film is formed by exciting the noble gas such as argon, helium, krypton, etc. introduced from the above by the high frequency source 14. When the insulating film is a silicon oxide film, silane gas is introduced into the line 13A, nitrous oxide gas is introduced into the line 13B, nitrogen gas is introduced into the line 13C, and argon or helium introduced from the line 13R. The desired silicon oxide film is formed by exciting a rare gas such as krypton by the high-frequency source 14. If the insulating film is a silicon nitride film, the silane gas in the line 13A is ammonia line 13B (NH ₃₎ gas, nitrogen gas is introduced to the line 13C, Ya argon introduced from the line 13R The desired silicon nitride film is formed by exciting a rare gas such as helium or krypton by the high-frequency source 14. Further, when the insulating film is a low dielectric constant silicon carbide film (SiOC film), tetramethylcyclotetrasilane (TOMCATS) gas is introduced into the line 13A, and carbon dioxide gas is introduced into the line 13B. The desired low-kSiOCH film is formed by exciting the introduced rare gas such as argon, helium, or krypton by the high-frequency source 14.

  In the film forming process of Step 2, at the same time as forming a desired film on the substrate W, the inner wall surface of the processing vessel 11, the surface of the shower head 13, and the surface of the susceptor 12 are also formed. A precipitate 33 having the same composition as that of the film is deposited as shown in FIG.

  Further, after Step 2, in Step 3, the gate valve 13G is opened, and the substrate W to be processed is unloaded from the processing container 11 through the gate valve 13G. After unloading the substrate to be processed W, the gate valve 13G is closed. Thereby, the film formation on the substrate W to be processed is completed.

Next, in step 4, in the processing container 11 and then in step 4, in the processing container 11, together with a rare gas such as argon gas, helium gas, krypton gas from the line 13R, NF is supplied from another line 13D. Etching gas containing F such as ₃ or CF ₄ is introduced as a cleaning gas.

  In step 4, the high frequency source 14 is further driven to excite the rare gas released into the processing space 11B with a high frequency of, for example, 400 kHz, thereby forming the plasma 11P in the same manner as in the previous step 2. Then, cleaning is performed to remove the deposit 33 by the etching action of F active species such as F radicals excited by plasma. As a result of such cleaning, the first and second coating films 31 and 32 are also removed, and the inner wall surface 11W of the processing vessel 11 is in a state where the AlF modified layer 11F previously shown in FIG. 3A is exposed. Return. Similar cleaning is performed on the shower head 13 and the susceptor 12.

  Further, after the cleaning process of Step 4, a process of forming the first and second coating films 31 and 32 on the inner wall surface 11W of the processing container W is performed as described above, and the process is performed. Returning to the step 1, processing of the next substrate to be processed W is started.

  In this embodiment, until the deposit 33 is deposited on the coating film 32 in step 2 of FIG. 4, the coating film 32 is accelerated electrons and ions in plasma as shown in FIG. However, in this embodiment, the coating film 32 is composed of a SiC film that is physically and chemically stable because of its high hardness and high binding energy. Can withstand even when exposed to various accelerating particles and does not disappear.

  On the other hand, since the coating film 31 made of the silicon oxide film thereunder is formed by the plasma CVD method as described above, it may contain defects such as dangling bonds and impurities. Since it has excellent adhesion to the modified layer 11F and has a low elastic modulus and easily deforms, it acts as an excellent stress relaxation layer between the inner wall surface 11W and the coating film 32. Therefore, the coating film 32 is held with high adhesion on the inner wall surface 11W. Even if the coating film 32 partially disappears, the substrate film W is sputtered from the inner wall surface 11W of the processing container 11 because the underlying coating film 31 protects the inner wall surface 11W of the processing container 11. The problem of being contaminated by the deposited Al does not occur.

  FIG. 7 shows the substrate processing apparatus of FIG. 1, after sequentially executing silicon nitride films on the 25 substrates to be processed W (# 1 to # 25) according to the flowcharts of FIGS. 8A to 8C. # 1, # 5, # 10, # 15, # 20, # 25, the number of particles having a particle size of 0.1 μm or more and particles having a particle size of 0.2 μm or more It is a figure which shows the number of. However, in FIG. 7, Experimental Example A is a comparative example in which no coating film is formed on the inner wall surface 11W of the processing vessel 11, and Experimental Example B is a coating made of the silicon oxide film on the inner wall surface 11W of the processing vessel 11. In the case where only the film 31 is formed, the experimental example C further explains the coating film 31 made of the silicon oxide film and the coating film 32 made of the silicon carbide film in this order on the inner wall surface 11W of the processing vessel 11 in this order. The case where it formed on the conditions which did is shown.

Referring to FIG. 8A, in Experiment A, first, in step 11, dry cleaning using NF ₃ gas is performed in the processing vessel 11 under the conditions described above, and then the sidewall surface 11W is reformed with AlF. Step 12 is executed in a state where the layer 11F is formed, and film formation corresponding to Step 2 in FIG. 4 is performed on the substrate W to be processed. Further, Steps 11 and 12 are repeated to process the substrates to be processed # 1 to # 25.

In experiment B, as shown in FIG. 8B, first, in step 21, dry cleaning using NF ₃ gas is performed in the processing vessel 11 under the conditions described above, and then AlF modification is performed on the side wall surface 11W. Step 22 is executed in a state in which the quality layer 11F is formed, and the first coating film 31 made of a silicon oxide film is formed on the inner wall surface 11W of the processing vessel 11 under the conditions described in Step 5 of FIG. It is formed with. Further, in step 23, film formation corresponding to step 2 in FIG. 4 is performed on the substrate W to be processed, and steps 21 to 23 are repeated to process the substrates W # 1 to # 25.

In experiment C, as shown in FIG. 8C, first, in step 31, dry cleaning using NF ₃ gas is performed in the processing vessel 11 under the conditions described above, and then AlF modification is performed on the side wall surface 11W. Step 32 is executed in a state in which the quality layer 11F is formed, and the first coating film 31 made of a silicon oxide film is formed on the inner wall surface 11W of the processing vessel 11 under the conditions described in Step 5 of FIG. In step 33, the second coating film 32 made of a silicon carbide film is formed on the first coating film 31 under the conditions described in step 5 of FIG. Further, in step 34, film formation corresponding to step 2 of FIG. 4 is performed on the substrate to be processed W, and steps 31 to 34 are repeated to process the substrates to be processed # 1 to # 25.

  Referring to FIG. 7, it can be seen that the number of particles having a particle size of 0.2 μm or more is suppressed to approximately 20 or less in any of the experimental examples, but is minimized in the case of Experimental Example C. . On the other hand, looking at the number of particles having a particle size of 0.1 μm or more, in Example A, the number of particles is very large, from 20 to 80 particles, and the variation is large, and the particle size is between 0.1 μm and 0.2 μm. It is shown that the occurrence of has not been suppressed. Furthermore, in Experimental Example B, the number of particles having a particle diameter of 0.1 μm or more exceeds 10 on average, although it is greatly improved compared to Experimental Example A, it reaches nearly 20 at the maximum. I understand.

  On the other hand, in Experimental Example C, as described above, not only the average number of particles having a particle size of 0.2 μm or more is 10 or less, but also the average number of particles having a particle size of 0.1 μm or more. The number of particles is 5 or less and at most 10 or less, and it is shown that generation of particles having a particle diameter in the range of 0.1 μm to 0.2 μm is effectively suppressed.

  Thus, according to this embodiment, as a result of performing the cleaning process using the etching gas containing F on the side wall surface 11W of the processing vessel 11 made of Al or Al alloy, the modified layer 11F such as AlF is formed. However, a coating film having high adhesion and high resistance to plasma can be formed on the silicon oxide film 31 and the silicon carbide film 32, and particle generation can be suppressed. In addition, it is possible to suppress the problem of metal contamination caused by sputtering due to plasma on the side wall surface 11W of the processing vessel 11.

[Second Embodiment]
FIG. 9 shows a modification of the semiconductor manufacturing method shown in the flowchart of FIG. However, in FIG. 9, the same reference numerals are assigned to the portions corresponding to the portions previously described in FIG.

  Referring to FIG. 9, in this embodiment, when film formation on one substrate W to be processed is completed in Step 3, in Step 3A, the cumulative number of film thicknesses of the substrate W to be processed so far is obtained. However, if the predetermined number is not reached (No), the process returns to step 1 and the steps 1 to 3 are repeated for the next substrate W to be processed. . On the other hand, if the predetermined number of substrates to be processed W have been processed in step 3A (YES), the process proceeds to the next steps 4 and 5, and the first and second coating films 31 and 32 are cleaned. The deposits thereon are removed together, and the first and second coating films 31 and 32 are newly formed.

  In the process of FIG. 9, since the new formation of the first and second coating films 31 and 32 is collectively performed for a predetermined number of substrates to be processed, the substrate W to be processed shown in the flowchart of FIG. Compared with the method of forming the first and second coating films 31 and 32 on each sheet, the manufacturing throughput of the semiconductor device can be improved.

  The silicon carbide film, silicon oxide film, silicon nitride film, and SiOC film formed on the target substrate W in the first and second embodiments are, for example, low dielectric constant layers constituting a multilayer wiring structure in a semiconductor device. Used as an insulating film.

  In the above description, the second coating film 32 is not limited to a silicon carbide film, but is composed of a silicon nitride film having a hardness higher than that of the silicon oxide film constituting the first coating film 31. Also good. Formation of such a silicon nitride film can be performed under the conditions described above in connection with film formation on the substrate W to be processed.

  Although the present invention has been described with respect to the case where the so-called parallel plate type plasma processing apparatus of FIG. 1 is used, the present invention is not limited to such a parallel plate type plasma processing apparatus. The same applies to a plasma processing apparatus, an ECR type plasma processing apparatus, a remote plasma processing apparatus, or a microwave plasma processing apparatus.

  Furthermore, in the present invention, it is also possible to apply a cleaning method using other halogens such as Br and Cl other than F.

  As mentioned above, although this invention was described about preferable embodiment, this invention is not limited to this specific embodiment, A various deformation | transformation and change are possible within the summary described in the claim.

DESCRIPTION OF SYMBOLS 10 Plasma CVD apparatus 11 Processing container 11A Exhaust port 11B Processing space 11F AlF modified layer 11P Plasma 11W Inner wall surface 12 Susceptor 13 Shower head 13A-13D, 13R Gas line 13G Gate valve 14 High frequency source 21, 33 Precipitate 31 1st Coating film 32 Second coating film

Claims (5)

(A) forming a first coating film made of a silicon oxide film on the inner wall surface of the processing vessel made of aluminum or an aluminum alloy and having an aluminum fluoride layer formed on the inner wall surface;
After the step (A), forming a second coating film made of a film having a hardness higher than that of the silicon oxide film on the first coating film;
(C) After the step (B), carrying a substrate to be processed into the processing container and placing it on a susceptor;
(D) After the step (C), introducing a processing gas into the processing container, and forming an insulating film on the surface of the substrate to be processed placed on the susceptor by a vapor deposition method; Including,
(E) After the step (D), a cleaning step is performed in which an etching gas containing fluorine is introduced into the processing container, and the first coating film and the second coating film are removed by etching. A method for manufacturing a semiconductor device.   2. The method of manufacturing a semiconductor device according to claim 1, wherein the step (E) is performed after the steps (A) to (D) are repeated a plurality of times.   3. The method of manufacturing a semiconductor device according to claim 1, wherein the second coating film is made of a silicon carbide film.   The first coating film is made of a silicon oxide film having a thickness of 100 nm to 300 nm, and the second coating film is made of a silicon carbide film having a thickness of 100 nm to 300 nm. 4. A method of manufacturing a semiconductor device according to claim 1.   The method of manufacturing a semiconductor device according to claim 1, wherein the vapor phase growth method is performed by exciting plasma.

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