Film forming method and film forming system

Abstract

Disclosed is a film forming method for forming a film using a batch type film forming apparatus that has a first chamber and a single-type modification apparatus that has a second chamber, the film forming method including: carrying a plurality of substrates into the first chamber; forming a compound film on the plurality of substrates carried into the first chamber; forming a carbon-containing protective film on the plurality of substrates in the first chamber; carrying out the plurality of substrates on which the protective film is formed, from the first chamber; carrying one to several substrates among the plurality of substrates carried out from the first chamber into the second chamber of the single-type modification apparatus; and subjecting the one to several substrates to a modification treatment in the second chamber. According to the present invention, a modified film is formed by performing the modification treatment.

Description

Film formation method and film formation system

[0001] The present disclosure relates to a film deposition method and a film deposition system.

[0002] Semiconductor devices include insulating films, hard masks, and the like, and compound films such as silicon nitride films (SiN films) are often used for these.

[0003] Known techniques for forming SiN films include a technique for simultaneously forming films on multiple substrates by plasma-assisted atomic layer deposition (ALD) using a vertical batch-type apparatus (e.g., Patent Document 1), and a technique for forming films on each substrate by plasma-assisted ALD using a single-wafer apparatus (e.g., Patent Document 2).

[0004] Japanese Patent No. 6656103 Japanese Patent Application Laid-Open No. 2019-163497

[0005] The present disclosure provides a film formation method and a film formation system that can form a compound film such as a SiN film with high productivity and good film quality.

[0006] A film formation method according to one aspect of the present disclosure is a film formation method for forming a film using a batch-type film formation apparatus having a first chamber and a single-wafer type modification apparatus having a second chamber, the method comprising: loading a plurality of substrates into the first chamber; depositing a compound film on the plurality of substrates loaded into the first chamber; forming a protective film containing carbon on the plurality of substrates in the first chamber; unloading the plurality of substrates on which the protective film has been formed from the first chamber; loading one or more substrates from the plurality of substrates unloaded from the first chamber into the second chamber of the single-wafer type modification apparatus; and performing a modification process on the one or more substrates in the second chamber, whereby a modified film is formed by performing the modification process.

[0007] According to the present disclosure, a film formation method and a film formation system are provided that are capable of forming a compound film such as a SiN film with high productivity and good film quality.

[0008] 1 is a flowchart showing a first embodiment of a film formation method; FIG. 2 is a process cross-sectional view showing an example of main steps of the first embodiment of the film formation method; FIG. 3 is a process cross-sectional view showing another example of main steps of the first embodiment of the film formation method; FIG. 4 is a process cross-sectional view showing yet another example of main steps of the first embodiment of the film formation method; FIG. 5 is a flowchart showing a second embodiment of a film formation method; FIG. 6 is a process cross-sectional view showing an example of main steps of the second embodiment of the film formation method; FIG. 7 is a block diagram schematically showing an example of a film formation system used to implement a film formation method; FIG. 8 is a vertical cross-sectional view showing an example of a batch-type film formation apparatus in the film formation system of FIG. 7; FIG. 9 is a horizontal cross-sectional view of the batch-type film formation apparatus shown in FIG. 8; FIG. 10 is a vertical cross-sectional view showing an example of a single-wafer type modification apparatus in the film formation system of FIG. 7;

[0009] Hereinafter, embodiments will be described with reference to the accompanying drawings.

[0010] <Film Forming Method> [First Embodiment] First, a first embodiment of a film forming method will be described. Fig. 1 is a flowchart showing the first embodiment of the film forming method, and Fig. 2 is a cross-sectional view showing main steps of the first embodiment of the film forming method.

[0011] In the first embodiment, a film is formed using a film formation system including a batch-type film formation apparatus having a first chamber and a single-wafer type modification apparatus having a second chamber.

[0012] A batch-type film formation apparatus is a film formation apparatus that performs film formation processing on a plurality of substrates, approximately 50 or more, at the same time. As a batch-type film formation apparatus, a vertical film formation apparatus can be used, in which a plurality of substrates (e.g., approximately 50 to 175 substrates) are stacked vertically and arranged in a chamber to perform film formation.

[0013] A single-wafer processing apparatus is an apparatus that performs a processing process on a single substrate or on several substrates (approximately up to four) on the same plane. As a single-wafer processing apparatus, an apparatus that has a stage provided in a chamber and places one or several substrates on the stage to perform the processing can be used.

[0014] First, a plurality of substrates are loaded into a first chamber of a batch-type film forming apparatus (step ST1). As shown in Fig. 2(a), the substrate S has a base body 201. Other films may be formed on the base body 201. The base body 201 is not particularly limited, but a semiconductor base body such as silicon is exemplified as a typical example.

[0015] Next, compound films are formed on the substrates loaded into the first chamber by ALD (step ST2). The compound films may be nitrogen-containing films or oxygen-carbon-containing films. In this embodiment, the formed compound films and the modified compound films have substantially the same composition, except for impurities. Film formation by ALD is performed by alternately supplying source gases and reactive gases to the first chamber, and repeating the adsorption of the source gases and the reaction with the reactive gases. Figure 2(b) shows the state in which a compound film 202 has been formed on the base 201 of the substrate S shown in Figure 2(a). While the case of forming a compound film by ALD has been illustrated here, a compound film may also be formed by CVD.

[0016] Examples of the compound film include those used as insulating films, hard masks, etc. When the compound film is a film containing nitrogen, it may be any of a SiN film, a SiCN film, a SiON film, a SiOCN film, a BN film, and a BCN film, and when it is a film containing oxygen and carbon, it may be a SiOC film. A SiOCN film is also a film containing oxygen and carbon.

[0017] In the case of SiN films, SiCN films, SiON films, SiOCN films, and SiOC films, a Si source gas is used as the source gas. The Si source gas may contain oxygen, nitrogen, or carbon in the source gas molecular skeleton. Furthermore, as the reactive gas, a nitrogen-containing gas is used for SiN films, a nitrogen-containing gas and a carbon-containing gas are used for SiCN films, and a nitrogen-containing gas and an oxygen-containing gas are used for SiON films. Furthermore, a carbon-containing gas and an oxygen-containing gas are used for SiOC films, and a nitrogen-containing gas, a carbon-containing gas, and an oxygen-containing gas are used for SiOCN films. BN films and BCN films can be formed using a B source gas as the source gas, and a nitrogen-containing gas for BN films and a nitrogen-containing gas and a carbon-containing gas for BCN films as the reactive gas.

[0018] As the Si source gas, a silane compound gas, a chlorosilane compound gas, an aminosilane compound gas, a siloxane compound gas, an organosilicon compound gas, a TSA (trisilylamine) gas, or the like can be suitably used. As the silane compound gas, SiH ４ Gas and Si ２ H ６ Examples of the chlorosilane compound gas include SiH ２ Cl ２ Examples of suitable gases include dimethylaminosilane as an aminosilane-based gas, tetraethoxysilane (TEOS) as a siloxane-based compound gas, and dimethyldimethoxysilane (DMDMOS) as an organosilicon-based compound gas. When forming a SiN film, a Cl-containing Si compound gas such as a chlorosilane-based compound can be suitably used as the Si source gas. In addition, examples of suitable B source gases include B ２ H ６ Gas, BCl ３ Suitable examples of the nitrogen-containing gas include NH ３ Gas, N ２ The oxygen-containing gas may be O ２ Gas, H ２ O gas, H ２ O２ Gas, N ２ O gas, NO gas, etc. can be used. ２ H ４ Gas, C ２ H ２ Gas, C ２ H ６ Gas, C ３ H ６ A hydrocarbon gas such as a gas can be used.

[0019] The film formation may be performed by plasma-assisted ALD (or plasma-assisted CVD in the case of CVD film formation). The addition of energy from the plasma allows film formation to be performed at a lower temperature. In particular, when high energy is required for film formation, the use of plasma is advantageous. When film formation using plasma is performed, a batch-type plasma-assisted film formation apparatus equipped with a remote plasma source can be used.

[0020] Next, a protective film containing carbon is formed on the plurality of substrates after film formation in the first chamber (step ST3). Fig. 2(c) shows a state in which a protective film 203 containing carbon is formed on the substrate S after the compound film 202 has been formed.

[0021] The carbon-containing protective film functions as a film that prevents oxidation of the compound film. The presence of the carbon-containing protective film prevents oxidation of the nitrogen-containing film or the oxygen-carbon-containing film when the substrate is carried out into the atmosphere. The thickness of the carbon-containing protective film is preferably 10 nm or more from the viewpoint of obtaining an effective protective effect. Furthermore, in consideration of ease of removal, the thickness is preferably 100 nm or less.

[0022] A carbon film can be used as the carbon-containing protective film. The carbon-containing protective film can be easily formed by introducing a carbon-containing gas or the like into the first chamber of a batch-type film-forming apparatus. When the carbon-containing protective film is a carbon film, the carbon-containing gas can be introduced into the first chamber and deposited by CVD (Chemical Vapor Deposition). The carbon-containing gas can be C ２ H ４ Gas, C２ H ２ Gas, C ２ H ６ Gas, C ３ H ６ In addition to the carbon-containing gas, a rare gas such as Ar gas or He gas may be added.

[0023] The carbon-containing protective film may be formed by plasma-assisted CVD using plasma. The addition of energy from the plasma allows film formation at a lower temperature. Since the formation of a carbon film requires high energy, it is advantageous to use plasma.

[0024] Next, the plurality of substrates are unloaded from the first chamber (step ST4). The unloaded plurality of substrates may be exposed to the atmosphere.

[0025] Next, one or more substrates from the plurality of substrates unloaded from the first chamber are loaded into the second chamber of the single-wafer processing modification apparatus (step ST5).

[0026] Next, the carbon-containing protective film on the substrate is removed in the second chamber (step ST6). The carbon-containing protective film is removed using an oxygen-free gas. This process may be plasma ashing. FIG. 2(d) shows the removal of the carbon-containing protective film 203 shown in FIG. 2(c) by plasma ashing. Carbon-containing protective films, such as carbon films, can be removed relatively easily by plasma ashing. The reason why an oxygen-free gas is used to remove the carbon-containing protective film is that if the film is removed using an oxygen-containing gas, the surface of the film exposed after removal will be oxidized.

[0027] The oxygen-free gas used in plasma ashing is H ２ Gas and NH ３ A reducing gas such as N gas can be preferably used. ２Gases may be used. These may be used alone or in combination of two or more. As the plasma, various plasmas such as capacitively coupled plasma, inductively coupled plasma, and microwave plasma may be used.

[0028] Next, in the second chamber, the substrate from which the carbon-containing protective film has been removed is subjected to a modification process (step ST7). In this embodiment, the modification process is performed on the film exposed after the carbon-containing protective film has been removed, i.e., the compound film. As a result, part or all of the compound film becomes a modified film, i.e., a modified compound film. This modification process may be a plasma modification process using plasma. FIG. 2(e) shows the state in which the plasma modification process is performed on the surface of the compound film 202 exposed after the protective film 203 in FIG. 2(d) has been removed, and FIG. 2(f) shows the state in which a modified film 202a has been formed by the modification process. Note that FIG. 2(f) shows an example in which the entire compound film 202 has become the modified film 202a, but only a part of the film 202 may become the modified film 202a. The depth of the modified film 202a may be 20 nm or less.

[0029] In this embodiment, the modification treatment is a treatment for improving the film quality of a compound film formed by a batch-type film forming apparatus. Specifically, the modification treatment, particularly the plasma modification treatment, removes impurities present in the compound film and eliminates dangling bonds to improve the bonding state of the compounds that make up the compound film.

[0030] The gas used in the plasma modification process can be a rare gas. For example, Ar gas, He gas, or a mixture thereof can be used. A chemical gas can also be added to the rare gas. For example, H ２ Gas, NH ３ Gas, N ２ Gases, hydrocarbon gases, etc. can be used, and these can be used alone or in combination of two or more. When the compound film is a SiOC film or a SiOCN film, the chemical gas can be the above-mentioned one plus a gas containing oxygen, for example, O ２ Gas, H ２ O gas, H ２ O ２ Gas, N ２One or more of O gas and NO gas may be added. By adding an oxygen-containing gas, the amount of oxygen in the compound film can be adjusted. Various plasmas such as capacitively coupled plasma, inductively coupled plasma, and microwave plasma can be used for the plasma modification process.

[0031] By using the above-described film formation method, when a compound film, typically a compound film containing nitrogen or a compound film containing oxygen and carbon, is formed, it is possible to form the film with high productivity and good film quality.

[0032] Conventionally, when forming a SiN film by ALD, for example, if a batch-type film formation apparatus such as that disclosed in Patent Document 1 is used, productivity is high because film formation processing is performed on multiple substrates at once, but this is disadvantageous in terms of obtaining high-quality film quality through low-temperature film formation, which is currently in demand. In particular, in a batch-type plasma-assisted film formation apparatus used when forming a SiN film, due to the structure of the apparatus, remote plasma must be used as the plasma, which is disadvantageous in terms of forming high-quality SiN films through low-temperature film formation.

[0033] On the other hand, when forming a SiN film by ALD in a single-wafer deposition apparatus as in Patent Document 2, a high-quality SiN film can be formed even at low temperatures because direct plasma is used, but it is necessary to repeatedly form atomic layers by alternately supplying Si raw material and nitriding gas, which is disadvantageous in terms of productivity.

[0034] Therefore, in this embodiment, a compound film is formed on multiple substrates at once using a batch-type film formation apparatus, a protective film containing carbon for anti-oxidation is formed, and then a modification process is performed on one or several substrates using a dedicated single-wafer modification apparatus. This makes it possible to obtain high-quality compound films at low temperatures while maintaining high productivity. In other words, since the basic film formation process is performed using a batch-type film formation apparatus, productivity is high, and even if the quality of the compound film formed at this time is low, a high-quality compound film can be obtained by subsequent modification process using the single-wafer modification apparatus.

[0035] In this case, a modification process using a single-wafer modification apparatus is added to the film formation process using a batch-type film formation apparatus. However, since each modification process is performed in a batch process to a certain depth (<20 nm), sufficiently high productivity can be obtained compared to single-wafer film formation by atomic layer by ALD. Furthermore, since the formation of a carbon-containing protective film for oxidation prevention can be performed in a short time by introducing a carbon-containing gas into the batch-type film formation apparatus, sufficiently high productivity can be maintained even when this process is added. Furthermore, since this carbon-containing protective film is removed in a batch process by ashing in the single-wafer modification apparatus, sufficiently high productivity can be maintained even when a process for removing the protective film is added.

[0036] Furthermore, since the modification process is performed in a dedicated single-wafer modification apparatus after film formation, it can be performed under conditions (high power, low pressure, etc.) that cannot be performed in conventional single-wafer film formation apparatuses, allowing for a high degree of freedom in the modification process and enabling modification process to be performed to deeper positions. Furthermore, since the modification process is performed by batch processing to a certain depth (<20 nm) after the compound film is formed, the compound film acts as a protective film for the underlayer, and damage to the underlayer can be mitigated compared to conventional single-wafer ALD film formation apparatuses that process atomic layers at a time. Alternatively, for the same damage, stronger modification conditions can be selected.

[0037] 2(a) to 2(f) show an example in which a compound film 202 is formed on a planar substrate 201, a carbon-containing protective film 203 is formed, the protective film 203 is removed by plasma ashing, and then the compound film 202 is subjected to a plasma modification process to form a modified film 202a. However, the present invention is not limited to this, and film formation may also be performed using a patterned substrate, such as when embedding a substrate having recesses formed therein or when a compound film is formed on the surface of a substrate having recesses formed therein.

[0038] 3(a) to 3(f) show an example of filling a substrate having a recess formed therein. As shown in FIG. 3(a), a substrate 211 having a recess 211a is prepared. As shown in FIG. 3(b), a compound film 212, for example, a film containing nitrogen or a film containing oxygen and carbon, is formed to fill the recess 211a. Then, as shown in FIG. 3(c), a carbon-containing protective film 213 is formed on the compound film 212. As shown in FIG. 3(d), the protective film 213 is removed by plasma ashing. Next, as shown in FIG. 3(e), a plasma modification process is performed on the filled film 212 to form a modified film 212a as shown in FIG. 3(f). In this example, if the recess 211a is deep, it is preferable to appropriately set the modification conditions (power, pressure, etc.) so that the modification effect is achieved deep into the filled compound film 212.

[0039] 4(a) to 4(f) show examples in which a compound film is formed on the surface of a substrate having a recess formed thereon, but not completely filling the recess. As shown in FIG. 4(a), a substrate 211 having a recess 211a is prepared, as in FIG. 3(a). As shown in FIG. 4(b), a compound film 214, for example, a film containing nitrogen or a film containing oxygen and carbon, is formed. Then, as shown in FIG. 4(c), a carbon-containing protective film 215 is formed on the compound film 214. As shown in FIG. 4(d), the protective film 215 is removed by plasma ashing. Next, as shown in FIG. 4(e), a plasma modification process is performed on the compound film 214, forming a modified film 214a as shown in FIG. 4(f).

[0040] Second Embodiment Next, a second embodiment of the film forming method will be described. Fig. 5 is a flowchart showing the second embodiment of the film forming method, and Fig. 6 is a cross-sectional view showing the main steps of the second embodiment of the film forming method.

[0041] In this embodiment, similar to the first embodiment, film formation is performed using a film formation system including a batch-type film formation apparatus having a first chamber and a single-wafer type modification apparatus having a second chamber.

[0042] First, a plurality of substrates are loaded into a first chamber of a batch-type film forming apparatus (step ST11). As shown in Fig. 6A, the substrate S has a base body 221. Other films may be formed on the base body 221. The base body 221 is not particularly limited, but a semiconductor base body is exemplified as a typical example, as in the first embodiment.

[0043] Next, compound films are formed by ALD on multiple substrates loaded into the first chamber of the batch-type film forming apparatus (step ST12). As in the first embodiment, compound films may also be formed by CVD. In this embodiment, carbon from the protective film is mixed into the film during the modification process described below, so the compound film functions as a precursor to the modified film, and the composition of the film to be formed is determined based on the modified composition. The compound film in this embodiment may be a film that becomes a nitrogen-containing film or a film containing oxygen and carbon after modification. Specifically, in addition to the SiN film, SiCN film, SiON film, SiOCN film, BN film, BCN film, and SiOC film exemplified in the first embodiment, it may also be a SiO film. Figure 6(b) shows the state in which such a compound film 222 has been formed on the base 221 of the substrate S shown in Figure 6(a).

[0044] Next, a protective film containing carbon is formed on the plurality of substrates after film formation in the first chamber (step ST13). Fig. 6(c) shows a state in which a protective film 223 containing carbon is formed on the substrate S after the compound film 222 has been formed.

[0045] Next, the plurality of substrates are unloaded from the first chamber (step ST14), and the unloaded plurality of substrates may be exposed to the atmosphere.

[0046] Next, one or more substrates from the plurality of substrates unloaded from the first chamber are loaded into the second chamber of the single-wafer processing modifying apparatus (step ST15).

[0047] The above steps ST11 to ST15 are basically performed in the same manner as steps ST1 to ST5 in the first embodiment.

[0048] In this embodiment, the substrate with the carbon-containing protective film remaining is then subjected to a modification process in the second chamber (step ST16). This results in the carbon from the protective film being mixed into the compound film, forming a modified film. This modification process may be a plasma modification process using plasma. FIG. 6(d) shows the state in which the plasma modification process is performed with the protective film 223 remaining as shown in FIG. 6(c), and FIG. 6(e) shows the state in which a modified film 222a has been formed by the modification process. Note that while FIG. 6(e) shows an example in which the entire compound film 222 is modified as the modified film 222a, only a portion of the compound film 222 may be modified as the modified film 222a. The depth of the modified film 222a may be 20 nm or less.

[0049] In this embodiment, the modification treatment is also a treatment for improving the film quality of a compound film formed by a batch-type film forming apparatus. Specifically, the modification treatment, particularly the modification treatment using plasma, mixes carbon from the carbon-containing protective film into the compound film to adjust the film composition, and at the same time, removes impurities from the compound film and eliminates dangling bonds to improve the bonding state of the compounds that make up the compound film.

[0050] Since carbon is mixed into the compound film during the modification process in this way, for example, if the compound film is a SiN film or a SiON film, the modified film will be a SiNC film or a SiOCN film. Also, if the compound film is a BN film, the modified film will be a BCN film. If the compound film is a SiO film, the modified film will be a SiOC film. If the compound film is a SiCN film, a BCN film, a SiOC film, or a SiOCN film, and the formed film contains carbon, the composition of the modified film will shift to a carbon-rich one. The composition of the modified film can be adjusted by the thickness of the carbon-containing protective film and the conditions of the modification process.

[0051] The gas used in the plasma modification process can be a rare gas. For example, Ar gas, He gas, or a mixture thereof can be used. A chemical gas can also be added to the rare gas. For example, H ２ Gas, NH ３ Gas, N ２Gases and the like can be used, and these may be used alone or in combination of two or more. As the plasma for the plasma modification treatment, various plasmas such as capacitively coupled plasma, inductively coupled plasma, and microwave plasma can be used. Furthermore, when the compound film is a SiO film, a SiON film, a SiOC film, or a SiOCN film, in addition to the above-mentioned chemical gases, a gas containing oxygen for adjusting the oxygen content, such as O ２ Gas, H ２ O gas, H ２ O ２ Gas, N ２ O gas or NO gas may also be used.

[0052] In this embodiment, too, a compound film is formed on multiple substrates in a batch-type film formation apparatus, a carbon-containing protective film is then formed, and the substrates are then modified in a dedicated single-wafer modification apparatus.This makes it possible to obtain high-quality compound films at low temperatures while maintaining high productivity.

[0053] In this embodiment, it is possible to obtain the same effects as in the first embodiment. Furthermore, in this embodiment, the carbon-containing protective film is not removed, and therefore productivity can be increased accordingly.

[0054] <Film Forming System> Next, a film forming system for carrying out the above-described film forming method will be described. Fig. 7 is a block diagram showing an example of a film forming system used to carry out the film forming method. As shown in Fig. 7, the film forming system 100 includes a batch-type film forming apparatus 101 having a first chamber, a single-wafer type modification apparatus 102 having a second chamber, a transfer device 103, and a control device 104.

[0055] The batch-type film-forming apparatus 101 carries a plurality of substrates into a chamber and performs a film-forming process on the plurality of substrates in a vacuum atmosphere. As the batch-type film-forming apparatus 101, a vertical film-forming apparatus, as described below, can be used in which a plurality of substrates (e.g., about 50 to 175 substrates) are stacked vertically and arranged in a chamber (first chamber) to form a film thereon. The batch-type film-forming apparatus 101 may also be equipped with a plasma source.

[0056] The single-wafer processing modifier 102 places one or more substrates on which a film has been formed on a stage in a chamber (second chamber) and performs a modification process on the film on the substrate in a vacuum atmosphere. The single-wafer processing modifier 102 may be equipped with a plasma source. Furthermore, a plurality of single-wafer processing modifiers 102 may be provided.

[0057] The transfer device 103 transfers substrates in an atmospheric environment. Specifically, it transfers substrates into the batch-type film-forming apparatus 101, transfers substrates from the batch-type film-forming apparatus 101 to the single-wafer type modifying apparatus 102, and transfers substrates from the single-wafer type modifying apparatus 102. The transfer device 103 also removes substrates from a substrate holder (not shown) that holds the substrates and transfers the substrates to the substrate holder. The transfer device 103 may have a first transfer unit that collectively transfers and unloads multiple substrates (e.g., 5 to 25 substrates) held in the holder into and out of the batch-type film-forming apparatus 101, and a second transfer unit that transfers and unloads substrates one or several at a time into and out of the single-wafer type modifying apparatus 102.

[0058] The control device 104 has a CPU (computer) and controls the batch type film forming apparatus 101, the single wafer type modifying apparatus 102, and the transport device 103. The control device 104 causes the batch type film forming apparatus 101, the single wafer type modifying apparatus 102, and the transport device 103 to perform operations for film formation based on a processing recipe.

[0059] In this film formation system 100, under the control of the control device 104, first, a plurality of substrates (e.g., 50 to 175 substrates) are loaded into the first chamber of the batch-type film formation apparatus 101 by the transfer device 103. Then, a compound film is formed on the plurality of substrates in the first chamber, followed by the formation of a carbon-containing protective film. Next, the transfer device 103 unloads the plurality of substrates from the first chamber of the batch-type film formation apparatus 101, and one or more of the substrates are loaded into the second chamber of the single-wafer type modifying apparatus 102. Next, when implementing the film formation method of the first embodiment, the carbon-containing protective film is removed from the substrates in the second chamber of the single-wafer type modifying apparatus 102, followed by a substrate modification process. Furthermore, when implementing the film formation method of the second embodiment, the substrates are modified in the second chamber of the single-wafer type modifying apparatus 102, leaving the carbon-containing protective film remaining on the substrates. After the substrate modification process is completed, the substrates are unloaded from the second chamber. The processing in the single-wafer processing modification apparatus 102 is repeated until the modification processing is performed on all of the plurality of substrates carried out from the batch-type film forming apparatus 101 .

[0060] The film formation system is not limited to a system configured as an integrated, clear system as shown in FIG. 7 , but may be any system capable of implementing the film formation method of the first or second embodiment. For example, even if a batch-type film formation apparatus and a single-wafer processing apparatus exist as separate systems and do not appear to be integrated, they are still considered a film formation system as long as they can implement the above-described method. In other words, even if the batch-type film formation apparatus and the single-wafer processing apparatus exist as separate systems and substrates are transported between the apparatuses using a transport container called a FOUP (Front Opening Unified Pod), they are still considered to constitute a film formation system as long as they can implement the above-described film formation method. In this case, for example, a host computer in a semiconductor factory may control film formation by the batch-type film formation apparatus, modification by the single-wafer processing apparatus, and substrate transport.

[0061] [Example of a Batch-Type Film Forming Apparatus] Next, an example of a batch-type film forming apparatus 101 will be described. Here, a film forming apparatus for forming a SiN film will be described as an example. Fig. 8 is a vertical cross-sectional view showing an example of the batch-type film forming apparatus 101, and Fig. 9 is a horizontal cross-sectional view of the batch-type film forming apparatus shown in Fig. 8.

[0062] The batch-type film formation apparatus 101 of this example is configured as a plasma-assisted vertical film formation apparatus and has a cylindrical first chamber 1 with a ceiling and an open bottom end. The entire first chamber 1 is made of, for example, quartz, and a quartz ceiling plate 2 is provided near the upper end of the first chamber 1 to seal the area below it. A cylindrical metal manifold 3 is connected to the opening at the lower end of the first chamber 1 via a sealing member 4 such as an O-ring.

[0063] The manifold 3 supports the lower end of the chamber 1, and a quartz substrate holder 5 carrying a plurality of substrates S, for example, 50 to 175 substrates S, stacked in multiple stages, is inserted into the first chamber 1 from below the manifold 3. The substrates S may be semiconductor wafers (silicon wafers), and the substrate holder 5 may be a wafer boat. The substrate holder 5 has three rods 6 (see FIG. 9), and the plurality of substrates S are supported by grooves (not shown) formed in the rods 6.

[0064] The substrate holder 5 is placed on a table 8 via a quartz heat-insulating tube 7, and the table 8 is supported on a rotating shaft 10 that passes through a metal (stainless steel) lid 9 that opens and closes the lower end opening of the manifold 3.

[0065] A magnetic fluid seal 11 is provided at the penetration portion of the rotating shaft 10, rotatably supporting the rotating shaft 10 while sealing it airtight. A seal member 12 is interposed between the periphery of the lid portion 9 and the lower end of the manifold 3 to maintain the sealing performance inside the first chamber 1.

[0066] The rotation shaft 10 is attached to the tip of an arm 13 supported by an elevation mechanism (not shown), and the substrate holder 5, lid 9, etc. are raised and lowered together to be inserted into and removed from the first chamber 1. Note that the table 8 may be fixed to the lid 9 side, so that film formation on the substrate S can be performed without rotating the substrate holder 5.

[0067] The batch-type film forming apparatus 101 also has a Si source gas supply mechanism 14 that supplies a Si source gas into the first chamber 1, a nitrogen-containing gas supply mechanism 15 that supplies a nitrogen-containing gas into the first chamber 1, and a carbon-containing gas supply mechanism 16 that supplies a carbon-containing gas into the first chamber 1. The batch-type film forming apparatus 101 also has an inert gas supply mechanism 29 that supplies an inert gas, for example, Ar gas, into the first chamber 1.

[0068] The Si source gas supply mechanism 14 includes a Si source gas supply source 17, a gas pipe 18 for introducing the Si source gas from the Si source gas supply source 17, and a gas dispersion nozzle 19 connected to the gas pipe 18 for introducing the Si source gas into the first chamber 1. The Si source gas is SiH ２ Cl ２ A Cl-containing Si compound gas such as a gas can be suitably used.

[0069] The nitrogen-containing gas supply mechanism 15 includes a nitrogen-containing gas supply source 20, a gas pipe 21 for introducing the nitrogen-containing gas from the nitrogen-containing gas supply source 20, and a gas dispersion nozzle 22 connected to the gas pipe 21 for introducing the nitrogen-containing gas into the first chamber 1. The nitrogen-containing gas may be, for example, NH ３ Gas, N ２ Gas may be used, or both of these may be used.

[0070] The carbon-containing gas supply mechanism 16 includes a carbon-containing gas supply source 23, a gas pipe 24 for introducing the carbon-containing gas from the carbon-containing gas supply source 23, and a gas dispersion nozzle 25 connected to the gas pipe for introducing the carbon-containing gas into the first chamber 1. The carbon-containing gas may be, for example, C ２ H ４ Gas, C ２ H ２ Gas, C ２H ６ Gas, C ３ H ６ A hydrocarbon gas such as a gas can be used.

[0071] Gas dispersion nozzles 19, 22, and 25 are made of quartz, penetrate inward through the sidewall of manifold 3, bend upward, and extend vertically. A plurality of gas discharge holes 19a, 22a, and 25a are formed at predetermined intervals in the vertical portions of gas dispersion nozzles 19, 22, and 25, respectively, over a length in the vertical direction corresponding to the substrate support range of substrate holder 5. Gas can be discharged approximately uniformly from each gas discharge hole 19a, 22a, and 25a in the horizontal direction toward first chamber 1. Note that although two gas dispersion nozzles 19 are provided in this example, only one may be provided.

[0072] The inert gas supply mechanism 29 includes an inert gas supply source 26, a gas pipe 27 for introducing inert gas from the inert gas supply source 26, and a gas nozzle 28 made of a short quartz tube connected to the gas pipe 27 and extending through the side wall of the manifold 3.

[0073] The gas pipes 18, 21, 24, and 27 are provided with on-off valves 18a, 21a, 24a, and 27a and flow rate controllers 18b, 21b, 24b, and 27b, respectively.

[0074] A plasma generation mechanism 30 is formed on a portion of the sidewall of the first chamber 1. The plasma generation mechanism 30 converts a nitrogen-containing gas and a carbon-containing gas into plasma and is configured as a remote plasma source. The plasma generation mechanism 30 includes a plasma partition wall 32 hermetically welded to the outer wall of the first chamber 1. The plasma partition wall 32 is formed, for example, from quartz. The plasma partition wall 32 has a concave cross section and covers an opening 31 formed in the sidewall of the first chamber 1. The opening 31 is elongated in the vertical direction so as to cover all of the substrates S supported by the substrate holder 5 in the vertical direction. A distribution nozzle 22 that discharges a nitrogen-containing gas and a distribution nozzle 25 that discharges a carbon-containing gas are disposed within the inner space defined by the plasma partition wall 32, i.e., the plasma generation space. Two gas distribution nozzles 19 are disposed outside the plasma generation space, sandwiching the opening 31 in the inner wall of the first chamber 1.

[0075] The plasma generation mechanism 30 further includes a pair of elongated plasma electrodes 33 arranged facing each other in the vertical direction on the outer surfaces of both side walls of the plasma partition wall 32, and a high-frequency power supply 35 connected to each of the pair of plasma electrodes 33 via a power supply line 34 and supplying high-frequency power to the pair of plasma electrodes 33. The high-frequency power supply 35 applies a high-frequency voltage of, for example, 13.56 MHz to the pair of plasma electrodes 33. This applies a high-frequency electric field to the plasma generation space defined by the plasma partition wall 32. The nitrogen-containing gas discharged from the distribution nozzle 22 and the carbon-containing gas discharged from the distribution nozzle 25 are converted into plasma in the plasma generation space to which the high-frequency electric field is applied, and the plasma gas containing activated species is transported into the first chamber 1 through the opening 31.

[0076] An insulating protective cover 36 is attached to the outside of the plasma compartment wall 32 so as to cover it. A coolant passage (not shown) is provided inside the insulating protective cover 36, and the plasma electrode 33 is cooled by flowing a coolant such as cooled nitrogen gas through the passage.

[0077] An exhaust port 37 for evacuating the first chamber 1 is provided in the sidewall of the first chamber 1 facing the distribution nozzles 19, 22, and 25. This exhaust port 37 is elongated in the vertical direction. An exhaust port cover member 38 having a U-shaped cross section is attached to the portion of the first chamber 1 corresponding to the exhaust port 37. This exhaust port cover member 38 extends upward along the sidewall of the first chamber 1 and defines a gas outlet 39 at the top of the first chamber 1. An exhaust device 40 including a vacuum pump or the like is connected to this gas outlet 39, and the first chamber 1 is evacuated via the gas outlet 39 by the exhaust device 40. A cylindrical heating mechanism 41 is provided surrounding the outer periphery of the first chamber 1 to heat the first chamber 1 and the multiple substrates S therein.

[0078] In such a batch-type film forming apparatus 101, a SiN film is formed as a compound film on a plurality of substrates S as follows, and then a carbon-containing protective film is formed thereon. The SiN film can be formed by, for example, ALD. The SiN film may also be formed by CVD.

[0079] First, the inside of the first chamber 1 is heated to a desired temperature, for example, 600°C or less, and the substrate holder 5 carrying 50 to 175 substrates S is loaded into the first chamber 1. The inside of the first chamber 1 is evacuated by the exhaust device 40 while the inside of the first chamber 1 is adjusted to a desired vacuum pressure.

[0080] Next, the supply of Si source gas from the Si source gas supply mechanism 14 to the first chamber 1 and the supply of plasmatized nitrogen-containing gas from the nitrogen-containing gas supply mechanism 15 to the first chamber 1 via the plasma generation mechanism 30 are repeated multiple times. In this way, a SiN film is formed by ALD, which alternately performs adsorption of the Si source gas onto the substrate S and nitriding of the adsorbed Si source gas. After each Si source adsorption process and each nitriding process, an inert gas is supplied from the inert gas supply mechanism 29 into the first chamber 1 to purge residual gas in the first chamber 1. When a SiN film is formed by CVD, the Si source gas and the nitrogen-containing gas are supplied simultaneously.

[0081] After the SiN film is formed, the first chamber is purged, and a carbon-containing protective film is formed. The carbon-containing protective film is formed by CVD by converting a carbon-containing gas supplied from a carbon-containing gas supply mechanism 16 into plasma using a plasma generation mechanism 30 and supplying the carbon-containing gas into the first chamber 1. Note that the carbon-containing protective film may be formed without converting the carbon-containing gas into plasma.

[0082] [Example of Single-Wafer Process Reformer] Next, a description will be given of an example of the single-wafer process reformer 102. FIG.

[0083] The single wafer modifying apparatus 102 of this example is a microwave plasma processing apparatus, and is configured as an RLSA (registered trademark) microwave plasma processing apparatus.

[0084] 10, the single-wafer reformer 102 has an airtight, grounded, substantially cylindrical second chamber 51. A circular opening 60 is formed in the approximate center of the bottom wall 51a of the second chamber 51, and an exhaust chamber 61 that communicates with this opening 60 and protrudes downward is provided in the bottom wall 51a.

[0085] A substrate mounting table 52 for horizontally supporting a substrate S is provided within the second chamber 51. The substrate mounting table 52 is made of ceramics such as AlN and is supported by a cylindrical support member 53 extending upward from the center of the bottom of the exhaust chamber 61. A guide ring 54 for guiding the substrate S is provided on the outer edge of the substrate mounting table 52. A resistance heating type heater 55 is embedded in the substrate mounting table 52, and the heater 55 receives power from a heater power supply 56 to heat the substrate mounting table 52 and control the temperature of the substrate S mounted thereon. An electrode 57 is embedded in the substrate mounting table 52, and a high-frequency power supply 59 for applying a bias is connected to the electrode 57 via a matching box 58.

[0086] The substrate mounting table 52 is provided with substrate support pins (not shown) for supporting and raising and lowering the substrate S, which can be protruded and retracted from the surface of the substrate mounting table 52 .

[0087] An annular gas inlet 65 is provided on the side wall of the second chamber 51, and a plurality of gas emission holes 65a are formed evenly in the gas inlet 65. A gas supply mechanism 66 is connected to the gas inlet 65.

[0088] The gas supply mechanism 66 supplies a rare gas, which is a plasma generating gas, used in the plasma modification process. Alternatively, a chemical gas for the plasma modification process or an oxygen-free gas used in plasma ashing to remove a protective film containing carbon may be supplied. H is used as the chemical gas for the plasma modification process. ２ Gas and NH ３ When a gas is used, it can also be used as an oxygen-free gas for plasma ashing. When multiple gases are supplied from the gas supply mechanism 66, the flow rates of the gases are independently controlled by flow rate controllers such as mass flow controllers through separate pipes and supplied to the gas inlet 65.

[0089] An exhaust pipe 73 is connected to the side of the exhaust chamber 61, and an exhaust device 74 including a vacuum pump, an automatic pressure control valve, etc. is connected to this exhaust pipe 73. By operating the vacuum pump of the exhaust device 74, the gas inside the second chamber 51 is uniformly discharged into the space 61a of the exhaust chamber 61 and exhausted through the exhaust pipe 73, and the inside of the second chamber 51 can be controlled to a predetermined vacuum level by the automatic pressure control valve.

[0090] A sidewall of the second chamber 51 is provided with a loading / unloading port 75 for loading / unloading the substrate S, and a gate valve 76 for opening / closing the loading / unloading port 75 .

[0091] The upper part of the second chamber 51 is an opening, and the periphery of the opening is a ring-shaped support part 77. A dielectric material such as quartz or Al is attached to the support part 77. ２ O ３ A circular microwave transmitting plate 78 made of ceramic such as a silicon dioxide gas or the like is provided airtightly via a sealing member 79. Therefore, the inside of the second chamber 51 is kept airtight.

[0092] A circular planar antenna 81 corresponding to the microwave transmitting plate 78 is provided above the microwave transmitting plate 78 so as to be in close contact with the microwave transmitting plate 78. This planar antenna 81 is fastened to the upper end of the side wall of the second chamber 51. The planar antenna 81 is configured as a circular plate made of a conductive material. Specifically, the planar antenna 81 is configured, for example, of a copper or aluminum plate with a silver- or gold-plated surface, with a number of microwave radiation holes 82 (slots) formed therethrough in a predetermined pattern. An example of such a pattern is a plurality of pairs of microwave radiation holes 82 arranged concentrically, each pair consisting of two microwave radiation holes 82 arranged in a T-shape. The length and spacing of the microwave radiation holes 82 are determined according to the wavelength (λg) of the microwave. For example, the microwave radiation holes 82 are arranged so that the spacing between them is λg / 4, λg / 2, or λg. The microwave radiation holes 82 may have other shapes, such as a circular or arc-shaped shape. Furthermore, the arrangement of the microwave radiation holes 82 is not particularly limited, and they may be arranged in a spiral or radial pattern in addition to a concentric pattern.

[0093] A slow-wave material 83 made of a dielectric having a dielectric constant greater than that of a vacuum, such as quartz, polytetrafluoroethylene, or a resin such as polyimide, is attached to and adhered to the top surface of this planar antenna 81. The slow-wave material 83 has the function of shortening the wavelength of the microwave compared to that in a vacuum, thereby reducing the size of the planar antenna 81. The slow-wave material 83 can adjust the phase of the microwave by its thickness, and by adjusting the thickness so that the joints of the planar antenna 81 form the "bells" of the standing wave, the radiation energy of the microwave can be maximized.

[0094] Although the planar antenna 81 and the microwave transmitting plate 78, and the wave retardation material 83 and the planar antenna 81 are arranged in close contact with each other, they may also be arranged at a distance from each other.

[0095] A shielding lid 84 made of a metal material such as aluminum, stainless steel, or copper is provided on the top surface of the second chamber 51 so as to cover the planar antenna 81 and the slow-wave member 83. The top surface of the second chamber 51 and the shielding lid 84 are sealed with a sealing member 85. A cooling water flow path 84a is formed in the shielding lid 84, and cooling water is passed through the flow path to cool the shielding lid 84, the slow-wave member 83, the planar antenna 81, and the microwave-transmitting plate 78. The shielding lid 84 is grounded.

[0096] An opening 86 is formed in the center of the upper wall of the shield lid 84, and a waveguide 87 is connected to this opening 86. A microwave generator 89 is connected to one end of this waveguide 87 via a matching circuit 88. As a result, microwaves having a frequency of, for example, 2.45 GHz generated by the microwave generator 89 are propagated to the planar antenna 81 via the waveguide 87. Note that various frequencies such as 8.35 GHz, 1.98 GHz, 860 MHz, and 915 MHz can be used as the microwave frequency.

[0097] The waveguide 87 includes a coaxial waveguide 87a with a circular cross section that extends upward from the opening 86 of the shield cover 84, and a horizontally extending rectangular waveguide 87b that is connected to the upper end of the coaxial waveguide 87a via a mode converter 90. The mode converter 90 between the rectangular waveguide 87b and the coaxial waveguide 87a has the function of converting microwaves propagating in TE mode within the rectangular waveguide 87b to TEM mode. An inner conductor 91 extends from the center of the coaxial waveguide 87a, and the lower end of this inner conductor 91 is fixedly connected to the center of the planar antenna 81. As a result, microwaves are uniformly and efficiently propagated to the planar antenna 81 via the inner conductor 91 of the coaxial waveguide 87a.

[0098] In such a single-wafer processing modifying apparatus 102 , first, the gate valve 76 is opened, and the substrate S is loaded into the second chamber 51 through the loading / unloading port 75 and placed on the substrate mounting table 52 .

[0099] Then, a rare gas, such as Ar gas, serving as a plasma generating gas is introduced into the second chamber 51 from the gas supply mechanism 66 via the gas inlet 65. Microwaves of a predetermined power are then guided from a microwave generator 89 to a waveguide 87 via a matching circuit 88. The microwaves guided into the waveguide 87 propagate through a rectangular waveguide 87b in TE mode. The TE mode microwaves are converted to TEM mode by a mode converter 90, and the TEM mode microwaves propagate through a coaxial waveguide 87a in TEM mode. The TEM mode microwaves then pass through the slow-wave material 83, the slot 82 of the planar antenna 81, and the microwave-transmitting plate 78, and are radiated into the second chamber 51. The microwaves spread as surface waves only in the region directly below the microwave-transmitting plate 78, generating surface wave plasma. The plasma then diffuses downward, resulting in a plasma with a high electron density and a low electron temperature in the region where the substrate S is located.

[0100] When removing the protective film containing carbon by plasma ashing, a high frequency bias for attracting ions is applied to the substrate mounting table 52 from the high frequency power supply 59, and H ２ Gas and NH ３ Reducing gases such as N２ A gas containing no oxygen, such as a gas containing no carbon, is supplied and turned into plasma, and the protective film containing carbon is removed by ashing.

[0101] When performing plasma modification processing, a high-frequency bias for attracting ions is applied to the substrate mounting table 52 from the high-frequency power supply 59, and further, a rare gas alone or a rare gas and H ２ Gas and NH ３ The plasma modification treatment is performed by supplying a chemical gas such as a carbon-containing gas to the substrate and converting the gas into plasma. As described above, the plasma modification treatment may be performed after removing the carbon-containing protective film, or may be performed while the carbon-containing protective film remains.

[0102] Although the embodiments have been described above, the disclosed embodiments should be considered to be illustrative and not restrictive in all respects. The above-described embodiments may be omitted, substituted, or modified in various ways without departing from the scope and spirit of the appended claims.

[0103] For example, in the above embodiments, the final film obtained is a film containing nitrogen or a film containing oxygen and carbon, but is not limited thereto. Furthermore, the methods for forming the compound film, forming the carbon-containing protective film, removing the protective film, and modifying the compound film are not limited to those exemplified in the embodiments. Furthermore, in the above embodiments, a plasma-assisted vertical batch-type film formation apparatus was shown as the batch-type film formation apparatus, but this is not limiting and a system that does not use plasma may also be used. Furthermore, while a system that uses microwave plasma was shown as the single-wafer modification apparatus, this is not limiting and other plasmas such as capacitively coupled plasma or inductively coupled plasma may also be used, or a system that does not use plasma may also be used.

[0104] 100; film formation system, 101; batch-type film formation apparatus, 102; single-wafer type modification apparatus, 103; conveyance device, 104; control device, 201, 211, 221; substrate, 202, 212, 222; compound film, 202a, 212a, 222a; modified film, 203, 213, 223; carbon-containing protective film, S; substrate

Claims

1. A film formation method for forming a film using a batch-type film formation apparatus having a first chamber and a single-wafer type modification apparatus having a second chamber, comprising: loading a plurality of substrates into the first chamber; depositing a compound film on the plurality of substrates loaded into the first chamber; forming a protective film containing carbon on the plurality of substrates in the first chamber; unloading the plurality of substrates on which the protective film has been formed from the first chamber; loading one or more substrates of the plurality of substrates unloaded from the first chamber into the second chamber of the single-wafer type modification apparatus; and performing a modification process on the one or more substrates in the second chamber, wherein a modified film is formed by performing the modification process.

2. The film formation method according to claim 1, wherein the batch-type film formation apparatus processes 50 or more substrates placed in the first chamber, and the single-wafer type modification apparatus processes one or a plurality of substrates, up to four substrates, placed on a stage in the second chamber.

3. The film forming method according to claim 1, further comprising removing the carbon-containing protective film in the second chamber to expose the compound film, and performing the modification treatment on the one or more substrates after removing the carbon-containing protective film.

4. The film forming method according to claim 3, wherein removing the carbon-containing protective film to expose the compound film is performed by plasma ashing using a gas not containing oxygen.

5. The film forming method according to claim 3, wherein the compound film is a film containing nitrogen or a film containing oxygen and carbon.

6. The film forming method according to claim 5, wherein the compound film is any one of a SiN film, a SiCN film, a SiON film, a SiOCN film, a BN film, a BCN film, and a SiOC film.

7. The film forming method according to claim 1, wherein the modification treatment is carried out while leaving the carbon-containing protective film on the one or more substrates.

8. The film forming method according to claim 7, wherein the modification treatment forms a modified film in which carbon from the carbon-containing protective film is mixed into the compound film.

9. The film forming method according to claim 8, wherein the composition of the compound film is determined so that the modified film is a film containing nitrogen or a film containing oxygen and carbon.

10. The film forming method according to claim 9, wherein the compound film is any one of a SiN film, a SiCN film, a SiON film, a SiOCN film, a BN film, a BCN film, a SiOC film, and a SiO film.

11. The film forming method according to any one of claims 1 to 10, wherein the thickness of the carbon-containing protective film is in the range of 10 nm to 100 nm.

12. The film forming method according to any one of claims 1 to 10, wherein the plurality of substrates removed from the first chamber are exposed to the atmosphere.

13. The method according to any one of claims 1 to 10, wherein the compound film is formed by plasma-assisted ALD.

14. The film formation method according to claim 13, wherein the compound film is formed using a vertical film formation apparatus as the batch-type film formation apparatus in which a plurality of substrates are stacked vertically and disposed in the first chamber to form a film.

15. The method of claim 14, wherein the plasma in the plasma-assisted ALD is a remote plasma.

16. The film formation method according to claim 13, wherein the step of forming the carbon-containing protective film is performed by plasma-assisted CVD by supplying a carbon-containing gas to the first chamber.

17. The film forming method according to any one of claims 1 to 10, wherein the modification treatment is carried out by a modification treatment using plasma.

18. The modification process using plasma is carried out by adding a rare gas or a rare gas and H ２ Gas, NH ３ Gas, N ２ 18. The film forming method according to claim 17, further comprising the step of adding one of a nitrogen gas and a hydrocarbon gas to the nitrogen gas.

19. A film formation system comprising: a batch type film formation apparatus having a first chamber and processing a plurality of substrates; a single wafer type modification apparatus having a second chamber and processing one or more substrates; a transport device for transporting substrates; and a control device, wherein the control device controls the batch type film formation apparatus, the single wafer type modification apparatus, and the transport device to perform the following: loading a plurality of substrates into the first chamber; depositing a compound film on the plurality of substrates loaded into the first chamber; forming a protective film containing carbon on the plurality of substrates in the first chamber; unloading the plurality of substrates on which the protective film has been formed from the first chamber; loading one or more substrates of the plurality of substrates unloaded from the first chamber into the second chamber of the single wafer type modification apparatus; and performing a modification process on the one or more substrates in the second chamber.

20. A film formation system for forming a compound film on a substrate, comprising: a batch-type film formation apparatus having a first chamber and processing a plurality of substrates; and a single-wafer type modification apparatus having a second chamber and processing one or more substrates, wherein a compound film is formed on the plurality of substrates in the first chamber, a protective film containing carbon is formed on the plurality of substrates on which the compound film is formed in the first chamber, one or more of the plurality of substrates on which the protective film is formed and removed from the first chamber are carried into the second chamber of the single-wafer type modification apparatus, and a modification process is performed on the one or more substrates in the second chamber.

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