JP2008034837A - Method for performing aftertreatment of amorphous carbon film, and method for manufacturing semiconductor device using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for performing aftertreatment of amorphous carbon film by which the behavior of the amorphous carbon film does not change a lot even if the treatment of the amorphous carbon film under heating, such as anneal, is performed after the amorphous carbon film is formed. <P>SOLUTION: Provided is the aftertreatment to be performed to the amorphous carbon film to which treatment including heating has been performed after the film is formed on a substrate. The treatment for preventing oxidation of the amorphous carbon film, for example, silylation treatment for contacting sililation reagent, is performed immediately after the treatment including heating. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a post-processing method for an amorphous carbon film suitable as a mask or the like for manufacturing a semiconductor device, and a method for manufacturing a semiconductor device using the same.

In a semiconductor device, an interlayer insulating film is formed between wiring layers. As such an interlayer insulating film, a SiO ₂ film has been conventionally used, but recently, a film having a lower dielectric constant has been demanded due to a demand for higher speed of a semiconductor device. For the rate film, for example, Si-based organic materials including Si, O, and C are being used.

  However, such a Si-based low dielectric constant film is expensive and has a problem that etching with high selectivity is difficult to perform with other films. A rate membrane is needed.

As such a material, an amorphous carbon film added with hydrogen has been studied. As shown in Patent Document 1, the amorphous carbon film can be formed by CVD using a hydrocarbon gas or the like as a processing gas, is inexpensive, and is similar to a Si-based low dielectric constant film. There is no inconvenience.
JP 2002-12972 A

  By the way, in the manufacturing process of a semiconductor device, heat treatment such as annealing treatment and other treatments are performed so that the final annealing process does not cause alteration or dimension change of each layer, or after a film is formed according to a process request. However, when such heat is applied to the amorphous carbon film, a part of the film is detached due to the bond of the relatively heat-sensitive part on the surface of the amorphous carbon film being cut. Release. When exposed to the atmosphere in this state, oxygen, moisture and the like react with the broken portion and are oxidized, and electrical characteristics such as dielectric constant and leakage current value, and refractive index are greatly changed. When such a characteristic change occurs, there arises a disadvantage that a desired device characteristic cannot be obtained.

  The present invention has been made in view of such circumstances, and an amorphous carbon film whose characteristics do not change greatly even when a process such as annealing is performed after the amorphous carbon film is formed. An object is to provide a post-processing method. In addition, a method for manufacturing a semiconductor device to which such a post-processing method is applied is provided. It is another object of the present invention to provide a computer-readable storage medium in which a control program for executing these methods is stored.

  According to a first aspect of the present invention, there is provided a post-processing method for an amorphous carbon film formed on a substrate and subjected to a treatment with heating, and the oxidation of the amorphous carbon film is prevented immediately after the treatment with heating. A post-processing method for an amorphous carbon film is provided.

  In the first aspect, a silylation treatment in which a silylating agent is brought into contact with the amorphous carbon film can be used as the treatment for preventing the oxidation.

  In the second aspect of the present invention, a step of forming an amorphous carbon film serving as an interlayer insulating film on a substrate, a step of performing a treatment with heating on the amorphous carbon film, and a step immediately after performing the treatment with heating. A step of bringing a silylating agent into contact with an amorphous carbon film to perform a silylation treatment, a step of heating the amorphous carbon film subjected to the silylation treatment to remove the silylating agent, and the removal of the silylating agent. And a step of quickly forming a predetermined film on the amorphous carbon film. A method for manufacturing a semiconductor device is provided.

  In the first and second aspects, the silylation treatment can be performed by bringing vapor of a silylating agent into contact with the surface of the amorphous carbon film. In this case, the silylation treatment can be performed at a temperature of room temperature to 200 ° C.

In the first and second aspects, the silylating agent is
HMDS (Hexamethyldisilan),
DMSDMA (Dimethylsilyldimethylamine),
TMSDMA (Dimethylaminotrimethylsilane),
TMDS (1,1,3,3-Tetramethyldisilazane),
TMSPyrole (1-Trimethylsilylpyrole),
BSTFA (N, O-Bis (trimethylsilyl) trifluoroacetamide),
BDDMMS (Bis (dimethylamino) dimethylsilane)
It is preferable that it is 1 type, or 2 or more types selected from the group consisting of.

  Furthermore, in the first or second aspect, as the treatment with heating, a typical example is an annealing treatment. The treatment with heating can be performed at 350 to 400 ° C.

  According to a third aspect of the present invention, there is provided a computer-readable storage medium in which a control program that operates on a computer is stored. The control program performs the method according to the first aspect at the time of execution. A computer-readable storage medium characterized by controlling a processing device is provided.

  According to a fourth aspect of the present invention, there is provided a computer-readable storage medium storing a control program that operates on a computer, and the control program is executed by the method for manufacturing a semiconductor device according to the second aspect. A computer readable storage medium is provided that controls a series of processing devices to be performed.

  According to the present invention, when a process involving heating such as annealing is performed on the amorphous carbon film, the silylating process is performed by contacting the amorphous carbon film with the silylating agent immediately after the process involving heating. Therefore, a highly polar functional group such as a hydroxyl group formed on the surface of the amorphous carbon film is replaced with a group containing silicon, and the surface is protected. Even if it is left as it is, functional groups such as hydroxyl groups do not increase with time, and characteristics such as electrical characteristics of the amorphous carbon film hardly deteriorate.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a flowchart showing a series of procedures including a post-processing method for an amorphous carbon film of the present invention, and FIG.

  First, a semiconductor wafer W in which, for example, a SiCO-based low dielectric constant film (Low-k film) 102 is formed as a base film on a silicon substrate 101 is prepared (Step 1, FIG. 2A), and then the base film 102 is prepared. An amorphous carbon film 103 is formed on the substrate (step 2, FIG. 2 (b)).

The method for forming the amorphous carbon film 103 is not particularly limited, but is preferably formed by CVD. As the processing gas at this time, propylene (C ₃ H ₆ ), propyne (C ₃ H ₄ ), propane (C ₃ H ₈ ), butane (C ₄ H ₁₀ ), butylene (C ₄ H ₈ ), butadiene ( A hydrocarbon gas such as C ₄ H ₆ ) or acetylene (C ₂ H ₂ ) or a gas mainly composed of these compounds can be used. For example, Japanese Patent Application Laid-Open No. 2002-12972 uses such a processing gas. The film can be formed by the method described in the publication. Further, by further containing oxygen as the processing gas, it is possible to form a strong carbon network even at a relatively low temperature.

After the amorphous carbon film 103 is formed, a process with heating such as an annealing process is performed (step 3, FIG. 2C). This treatment is performed under appropriate conditions depending on the semiconductor element to be obtained, and is typically about 350 to 400 ° C. in a non-oxidizing atmosphere (vacuum or an inert gas atmosphere such as Ar gas or N ₂ gas). Done.

The amorphous carbon film 103 immediately after the film formation has a healthy surface state and does not change with time even when taken out into the atmosphere. However, after the treatment with heating such as annealing treatment is performed in this way, the amorphous carbon film 103 A part of the film is detached due to, for example, the breakage of the relatively heat-sensitive part on the surface of the film 103. After the treatment with such heating, when exposed to the atmosphere in this state, oxygen and moisture react with the broken part in a relatively short time, and -C-C. + O ₂ →- Reactions such as C—C═O + O ^* —C—CH + O ^* → —C—C—OH, —C—C · + H ₂ O → —C—C—OH + H are oxidized, and carbonyl groups and A functional group having polarizability such as a hydroxyl group is formed, and such a functional group increases with time. Such a functional group adsorbs moisture, and greatly changes electric characteristics such as dielectric constant and other characteristics. For example, an amorphous carbon film has a relative dielectric constant k of about 2.8 when it is formed, whereas k = 2.6 to 2.7 immediately after annealing at about 400 ° C. Although the characteristics are once improved, the k value exceeds 3 and the leakage characteristics are deteriorated by leaving it in the atmosphere for about 100 hours or more. In addition, an increase in refractive index is also observed when left in the atmosphere for a long time.

  In order to prevent such a change in electrical characteristics and the like over time, a silylation treatment, which is a post-treatment of the present invention, is performed immediately after the treatment with heating in Step 3 (Step 4, FIG. 2 (d)). The silylation treatment is a treatment in which a functional group having polarizability such as a carbonyl group or a hydroxyl group formed on the surface of the amorphous carbon film 103 is reacted with a silylating agent to replace it with a group containing silicon. The surface of the carbon film is protected, and it is possible to prevent the functional groups such as hydroxyl groups from increasing over time and changing the characteristics. Immediately after such a silylation treatment, the value of the dielectric constant k slightly increases, but the value hardly changes even if it is left in the air thereafter. As for the refractive index, even if it is left in the air after the silylation treatment, its value hardly changes. Here, “immediately after the process with heating” may be after a period in which the characteristics hardly deteriorate after the process with heating.

As a silylating agent, any substance that causes a silylation reaction can be used without particular limitation, but a compound group having a silazane bond (Si-N bond) in the molecule has a relatively small molecular structure. Is preferred. Specifically, for example,
HMDS (Hexamethyldisilan),
DMSDMA (Dimethylsilyldimethylamine),
TMSDMA (Dimethylaminotrimethylsilane),
TMDS (1,1,3,3-Tetramethyldisilazane),
TMSPyrole (1-Trimethylsilylpyrole),
BSTFA (N, O-Bis (trimethylsilyl) trifluoroacetamide),
BDDMMS (Bis (dimethylamino) dimethylsilane)
Etc. can be used. These chemical structures are shown below.

  Taking the case of using DMSDMA as a silylating agent as an example, the silylation reaction is represented by the following chemical formula 2, and the OH group in the film is replaced with the O-Si form.

  The silylation treatment can be performed by bringing the silylating agent into contact with the amorphous carbon film, and typically includes bringing the silylating agent vapor into contact with the surface of the amorphous carbon film as described later. . The silylating agent may be applied to the amorphous carbon film.

  By performing the silylation treatment in this way, it is possible to prevent the deterioration of the characteristics of the amorphous carbon film even if the semiconductor substrate is left in the atmosphere. However, if the silylation treatment is performed, the next step is performed. Since a cap film or a metal film cannot be formed, the silylating agent on the surface of the amorphous carbon film is removed by heating prior to the next film formation (step 5, FIG. 2 (e)). The heat removal of the silylating agent is performed in a reduced pressure atmosphere of 133 Pa (1 Torr) or less, and a temperature of about 200 ° C. is sufficient at this time. By the heat removal of the silylating agent, the electrical characteristics such as the dielectric constant are returned to the characteristics after the treatment accompanied with the heating in Step 3.

After the step 5 of removing the silylating agent by heating, SiO ₂ , SiN, SiCN, SiCO functioning as a cap film or a hard mask, and Cu, Ti, Ta, W as metal films on the amorphous carbon film. The predetermined film 104 is formed (step 6, FIG. 2 (f)). In this case, since the characteristics of the amorphous carbon film are not deteriorated due to the protective effect by the silylation treatment, a device having good characteristics can be manufactured by a series of subsequent treatments.

  Next, an example of a method for manufacturing a semiconductor device including the above steps will be described. For example, when copper is buried using the dual damascene method, the semiconductor device having the structure shown in FIG. 3 is obtained by etching holes and trenches and filling a Cu film from the state shown in FIG. be able to. That is, after the silylating agent is removed by heating in FIG. 2 (e), a hard mask is formed as the film 104 to obtain the state shown in FIG. 2 (f), from which holes 105, amorphous carbon are formed in the Low-k film 102. A trench 106 is formed by etching in the film 103, and then a barrier film 107 and a Cu film 108 are formed.

  Next, a processing device group for carrying out a series of steps as shown in FIG. 1 will be described. FIG. 4 is a block diagram showing a processing device group for carrying out the series of steps. This processing apparatus group includes an amorphous carbon film forming apparatus 201 for forming an amorphous carbon film on a predetermined film formed on a semiconductor wafer, for example, a SiCO-based low dielectric constant film (Low-k film), and an amorphous carbon film. A heat treatment apparatus 202 for performing a heat treatment such as an annealing process on the semiconductor wafer on which the film is formed, a silylation treatment apparatus 203 for performing a silylation process on the amorphous carbon film in the semiconductor wafer after the heat treatment, and an amorphous in the silylation process A silylating agent removing device 204 for removing the silylating agent formed on the surface of the carbon film; and a film forming device 205 for forming a predetermined film on the amorphous carbon film after removing the silylating agent. Yes. Note that when the wafer W is transferred between the apparatuses, a transfer apparatus (not shown) is used. It may be conveyed by an operator.

  Each of these devices is configured to be collectively controlled by a process controller 211 having a microprocessor (computer). The process controller 211 includes a user interface 212 including a keyboard that allows a process manager to input commands to manage each device, a display that visualizes and displays the operating status of each device, and each processing device. Are connected to a storage unit 213 storing a recipe in which a control program for realizing various processes executed by the control of the process controller 211 and processing condition data are stored.

  Then, if necessary, in response to an instruction from the user interface 212, a desired recipe is called from the storage unit 213 and executed by the process controller 211. A series of processes are performed. The recipe may be stored in a readable storage medium such as a CD-ROM, a hard disk, a flexible disk, or a non-volatile memory. For example, it is possible to transmit the data as needed via a dedicated line and use it online.

Next, a silylation processing apparatus 203 that performs a silylation process that is a post-process of the amorphous carbon film will be described. FIG. 5 is a cross-sectional view showing a schematic configuration of the silylation processing apparatus. The silylation processing apparatus 203 includes a chamber 1 that accommodates a wafer W. The chamber 1 includes a fixed lower container 1a and a lid 1b that covers the lower container 1a, and the lid 1b is not shown. It can be raised and lowered by the device. The lower container 1 a is provided with a hot plate 2, and vapor of any of the above silylating agents is supplied into the chamber 1 from the periphery of the hot plate 2. The silylating agent is vaporized by the vaporizer 3 to be vaporized, is carriered by N ₂ gas, and is supplied to the chamber 1.

  A heater 2a is embedded in the hot plate 2, and the temperature can be adjusted, for example, in the range of room temperature to 200 ° C. by the heater 2a, and pins 4 for supporting the semiconductor wafer W are provided on the surface thereof. It has been. By not placing the semiconductor wafer W directly on the hot plate 2, contamination of the back surface of the wafer W is prevented. A first seal ring 5 is provided on the upper surface of the outer peripheral portion of the lower container 1a, and the lower surface of the outer peripheral portion of the lid body 1b contacts the first seal ring 5 when the lid body 1b is pressed against the lower container 1a. A second seal ring 6 is provided. Two pairs of the first and second seal rings 5 and 6 are provided on the inner side and the outer side, and the space between them can be depressurized. By depressurizing the space, the airtightness of the chamber 1 is reduced. Sex is secured. A substantially central portion of the lid 1b is provided with an exhaust port 7 for exhausting the silylating agent and nitrogen gas supplied to the chamber 1, and this exhaust port 7 is evacuated via a pressure adjusting device 8. It is connected to the pump 9.

In the silylation processing apparatus 203 configured as described above, the semiconductor wafer W is loaded into the chamber 1 with the lid 1 b raised and placed on the pins 4 of the hot plate 2. Next, the lid 1b is lowered to make the inside of the chamber 1 a sealed space, and the inside of the chamber 1 is further depressurized to improve airtightness. In this state, the hot plate 2 is controlled to a predetermined temperature of room temperature to 200 ° C. The temperature of the vaporizer 3 is set to room temperature to 50 ° C., the silylating agent is supplied at a flow rate of, for example, 0.1 to 1.0 g / min, and N ₂ gas (purge gas) is supplied at a flow rate of, for example, 1 to 10 L / min. Is 666-96000 Pa (5-720 Torr), and silylation is performed for about 1 minute. Thereby, the vapor | steam of a silylating agent is supplied on the amorphous carbon film formed in the semiconductor wafer W, a silylation reaction is produced on the surface, and a protective film is formed.

Next, experimental results for confirming the effects of the present invention will be described.
Here, the electrical characteristics (relative dielectric constant, leak current at the time of applying 1 MV) after various treatments were measured on the amorphous carbon film formed by CVD using the above-described hydrocarbon gas. These characteristics are shown as average values measured three times.

First, no. The dielectric constant and leakage current of the amorphous carbon film immediately after film formation as sample 1 were 2.84 and 1.52 × 10 ⁻⁸ A / cm ² , respectively. Next, no. When the relative permittivity and leakage current were measured as sample No. 2 after being left in the atmosphere for 100 hours after film formation, they were 2.87 and 1.17 × 10 ⁻⁸ A / cm ² , respectively. There wasn't. No. When the relative permittivity and the leakage current were measured as a sample No. 3 immediately after the film was formed and annealed at 400 ° C. for 30 minutes (in an Ar gas atmosphere), 2.61 and 1.39 × 10 ⁻⁹ A were obtained, respectively. / Cm ² , and these characteristics were improved.

No. As a sample of No. 4, after the annealing treatment was performed in this manner, the relative dielectric constant and the leakage current were measured after 100 hours in the atmosphere, and 3.05 and 8.56 × 10 ⁻⁹ A / cm ² , respectively. It was confirmed that the electrical characteristics deteriorated when left in the air after annealing. No. with the standing time extended to 200 hours. As a result of measuring the relative dielectric constant and the leakage current of the sample No. 5, the results were 3.33 and 3.76 × 10 ⁻⁸ A / cm ² , respectively. In the sample No. 6, the values were 5.73 and 8.69 × 10 ⁻⁶ A / cm ² , respectively, and it was confirmed that the deterioration of these characteristics became severe as the elapsed time after the annealing treatment became longer.

Next, no. Sample No. 7 was subjected to a baking process at 200 ° C. after 100 hours in the air after the annealing process, and as a result, the electrical characteristics were characterized. As a result, the relative dielectric constant was 3.12 and the leakage current was 2.66 × 10 ⁻⁹ A / No. ^{2 in} which no baking is performed. Although the leakage current was slightly improved compared to 4, the relative dielectric constant did not recover and it was confirmed to be insufficient. No. As a sample of No. 8, annealing was performed at 400 ° C. for 30 minutes in an atmosphere in which Ar gas was added with 10% H ₂ gas, and then left in the air for 200 hours. No. There leakage current 8.44 × ¹⁰ -9 a / cm ² becomes 3.29, without the addition of _{H 2} gas under the same conditions Although it was slightly better than 5, it was insufficient.

In contrast, no. As a sample of No. 9, No. 9 was formed after the amorphous carbon film was formed. After performing an annealing process at 400 ° C. for 30 minutes in an atmosphere containing 10% H ₂ gas, as in 8, the silylating apparatus shown in FIG. As a result of measuring the electrical characteristics after leaving it in the atmosphere for 200 hours, the relative dielectric constant was 2.87 and the leakage current was 4.52 × 10 ⁻⁹ A / cm ² . It was confirmed that the electrical characteristics were better than those of the 8 sample. That is, it was confirmed that the electrical characteristics hardly deteriorate even after being left in the atmosphere by performing silylation treatment on the amorphous carbon film after annealing. No. As 10 samples, no. After the silylation treatment of No. 9, annealing was performed at 400 ° C. for 30 minutes in an atmosphere in which 10% of H ₂ gas was added again, and then left in the atmosphere for 200 hours. As a result, the relative dielectric constant was 2.73. The current was 4.75 × 10 ⁻⁹ A / cm ² , and it was confirmed that the electrical characteristics were not improved by the ^second annealing. Furthermore, no. As a sample of No. 11, after forming an amorphous carbon film, The silylation treatment was performed under the same conditions as in No. 9, followed by annealing at 400 ° C. for 30 minutes in an atmosphere to which 10% of H ₂ gas was added. No. .45, the leakage current is 3.64 × 10 ⁻⁸ A / cm ² , and no silylation treatment is performed. It was confirmed that the electrical characteristics were not improved as compared with 8, and no effect was obtained even if the silylation treatment was performed before the annealing treatment.

  Based on the above, it was confirmed that the amorphous carbon film was annealed at about 400 ° C. after the amorphous carbon film was formed, and then the silylation process was performed. It was done. In the above experiment, the silylation treatment was performed at room temperature, but it is expected that the effect will be increased by increasing the temperature to about 100 to 200 ° C.

  In addition, this invention is not limited to the said embodiment, A various deformation | transformation is possible. For example, in the said embodiment, although the silylation process was illustrated as a process which prevents the oxidation of amorphous carbon, if it is a process which can prevent the oxidation of an amorphous carbon, it will not specifically limit. In the above embodiment, an example in which an amorphous carbon film is applied as an interlayer insulating film has been described. However, the present invention can also be applied to other uses such as an antireflection film. That is, it is important that the antireflective film has a specific refractive index, but after treatment with heating, the refractive index tends to increase with time by leaving it in the atmosphere. By preventing such a change in refractive index with time by post-processing, stable characteristics as an antireflection film can be obtained.

  In the above embodiment, it is assumed that the amorphous carbon film is left in the air after being subjected to a heat treatment such as annealing. However, the amorphous carbon film is not limited to the air and is left in an atmosphere containing oxygen and hydrogen to some extent. The effect can be obtained about the case.

  Furthermore, in the above embodiment, the semiconductor wafer is exemplified as the substrate to be processed. However, the present invention is not limited to this, and other substrates such as a glass substrate for a flat panel display (FPD) typified by a liquid crystal display device (LCD) can be used. Applicable.

  The present invention is suitable for applications that utilize the low dielectric constant characteristics of amorphous carbon films.

The flowchart which shows a series of procedures including the post-processing method of the amorphous carbon film of this invention. Process sectional drawing which shows a series of procedures including the post-processing method of the amorphous carbon film of this invention. Sectional drawing which shows the structural example obtained with the manufacturing method of the semiconductor device of this invention. The block diagram explaining the processing apparatus group which enforces the manufacturing method of the semiconductor device of this invention. Sectional drawing which shows schematic structure of the silylation processing apparatus in the processing apparatus group of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Chamber 2; Hot plate 2a; Heater 3; Vaporizer 7; Exhaust port 101; Silicon substrate 102; Low-k film 103; Amorphous carbon film 104; Film 105; Hole 106; Trench 107; 201; amorphous carbon film forming apparatus 202; heat treatment apparatus 203; silylation processing apparatus 204; silylating agent removing apparatus 205; film forming apparatus 211; process controller 212; user interface 213; storage unit W;

Claims (15)

A method for post-processing an amorphous carbon film formed on a substrate and subjected to a treatment with heating,
A method for post-processing an amorphous carbon film, wherein a process for preventing oxidation of the amorphous carbon film is performed immediately after the process with heating.   The method for post-processing amorphous carbon according to claim 1, wherein the treatment for preventing oxidation is a silylation treatment in which a silylating agent is brought into contact with the amorphous carbon film.   The method for post-processing an amorphous carbon film according to claim 2, wherein the silylation treatment is performed by bringing a vapor of a silylating agent into contact with the surface of the amorphous carbon film.   The post-treatment method for an amorphous carbon film according to claim 3, wherein the silylation treatment is performed at a temperature of room temperature to 200 ° C. The silylating agent is
HMDS (Hexamethyldisilan),
DMSDMA (Dimethylsilyldimethylamine),
TMSDMA (Dimethylaminotrimethylsilane),
TMDS (1,1,3,3-Tetramethyldisilazane),
TMSPyrole (1-Trimethylsilylpyrole),
BSTFA (N, O-Bis (trimethylsilyl) trifluoroacetamide),
BDDMMS (Bis (dimethylamino) dimethylsilane)
5. The post-treatment method for an amorphous carbon film according to claim 2, wherein the post-treatment method is one or more selected from the group consisting of:   6. The post-processing method for an amorphous carbon film according to claim 1, wherein the treatment with heating is an annealing treatment.   The method for post-processing an amorphous carbon film according to any one of claims 1 to 6, wherein the treatment with heating is performed at 350 to 400 ° C. Forming an amorphous carbon film as an interlayer insulating film on the substrate;
A step of subjecting the amorphous carbon film to a treatment with heating;
A step of bringing a silylating agent into contact with the amorphous carbon film immediately after the treatment with heating, and a silylation treatment;
Heating the amorphous carbon film subjected to the silylation treatment to remove the silylating agent;
And a step of forming a predetermined film on the amorphous carbon film immediately after removing the silylating agent.   9. The method of manufacturing a semiconductor device according to claim 8, wherein the silylation treatment is performed by bringing vapor of a silylating agent into contact with the surface of the amorphous carbon film.   10. The method of manufacturing a semiconductor device according to claim 8, wherein the silylation treatment is performed at a temperature of room temperature to 200 ° C. 10. The silylating agent is
HMDS (Hexamethyldisilan),
DMSDMA (Dimethylsilyldimethylamine),
TMSDMA (Dimethylaminotrimethylsilane),
TMDS (1,1,3,3-Tetramethyldisilazane),
TMSPyrole (1-Trimethylsilylpyrole),
BSTFA (N, O-Bis (trimethylsilyl) trifluoroacetamide),
BDDMMS (Bis (dimethylamino) dimethylsilane)
11. The method of manufacturing a semiconductor device according to claim 8, wherein the semiconductor device is one or more selected from the group consisting of:   The method for manufacturing a semiconductor device according to claim 8, wherein the treatment with heating is an annealing treatment.   The method for manufacturing a semiconductor device according to claim 8, wherein the treatment with heating is performed at 350 to 400 ° C. 13. A computer-readable storage medium storing a control program that runs on a computer,
A computer-readable storage medium, wherein when executed, the control program causes a computer to control a processing device so that the method of any one of claims 1 to 7 is performed. A computer-readable storage medium storing a control program that runs on a computer,
14. A computer-readable storage medium characterized in that, when executed, the control program causes a computer to control a series of processing devices so that the semiconductor device manufacturing method according to claim 8 is performed.

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