Method for depositing film and film deposition apparatus

Abstract

To provide a method for depositing a film that can selectively deposit an object film with high accuracy to a desired region in a substrate while suppressing damages, and to provide a film deposition apparatus.SOLUTION: A method for depositing a film includes steps of: providing a substrate with a first film and a second film different from the first film; selectively forming a graphene-containing film at a surface of the second film; processing the substrate on which the graphene-containing film has been deposited with a hydrogen-containing plasma; and selectively forming an object film at a surface of the first film.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a film forming method and a film forming apparatus. [Background technology]

[0002] Recently, with the progress of miniaturization of semiconductor devices, a technology that can realize selective film formation with higher accuracy than photolithography technology has been studied. As such a technology, a technology has been proposed in which a self-assembled monolayer (SAM) is formed as a film formation inhibitor on the surface of a substrate area where film formation is not desired, and a target film is formed only on the area of ​​the substrate surface where the SAM is not formed (for example, Patent Documents 1 and 2, Non-Patent Document 1).

[0003] On the other hand, a technology has been proposed that uses graphene as a material that inhibits the formation of a target film on a metal surface (Patent Documents 3 and 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2010-540773 [Patent Document 2] Special Publication No. 2013-520028 [Patent Document 3] JP 2018-182328 A [Patent Document 4] US Patent Application Publication No. 2022 / 0068704 [Non-patent literature]

[0005] [Non-Patent Document 1] Hashemi,FSM et.al ACS Appl. Mater.Interfaces 2016, 8(48),pp33264-33272, November 7, 2016 Summary of the Invention [Problem to be solved by the invention]

[0006] The present disclosure provides a film formation method and a film formation apparatus that are capable of selectively forming a target film on a desired region of a substrate with high precision while suppressing damage. [Means for solving the problem]

[0007] A film formation method according to one aspect of the present disclosure includes preparing a substrate having a first film and a second film different from the first film, selectively forming a graphene-containing film on a surface of the second film, treating the substrate after the graphene-containing film is formed with a hydrogen-containing plasma, and selectively forming a target film on a surface of the first film. Effect of the Invention

[0008] According to the present disclosure, there is provided a film formation method and a film formation apparatus that are capable of selectively forming a target film on a desired region of a substrate with high precision while suppressing damage. [Brief description of the drawings]

[0009] [Figure 1] 3 is a flowchart showing a film forming method according to the first embodiment. [Diagram 2] 1A to 1C are cross-sectional views illustrating process steps of a film forming method according to a first embodiment. [Diagram 3] 6 is a flowchart showing a film forming method according to a second embodiment. [Figure 4] 6A to 6C are cross-sectional views illustrating some of the steps of a film forming method according to a second embodiment. [Diagram 5] 10 is a flowchart showing a film forming method according to a third embodiment. [Figure 6] 10A to 10C are cross-sectional views illustrating some of the steps of a film forming method according to a third embodiment. [Figure 7] 1 is a schematic diagram illustrating an example of an overall configuration of a film formation apparatus capable of carrying out a film formation method according to an embodiment of the present invention. [Figure 8] FIG. 8 is a cross-sectional view showing an example of a graphene-containing film deposition module mounted in the film deposition apparatus of FIG. 7. [Figure 9] FIG. 9 is a cross-sectional view that illustrates a microwave radiation mechanism in the graphene-containing film deposition module of FIG. 8. [Figure 10] 9 is a bottom view diagrammatically illustrating a ceiling wall portion of a processing vessel in the graphene-containing film formation module of FIG. 8. FIG. [Figure 11] 8 is a cross-sectional view showing an example of a hydrogen-containing plasma processing module installed in the film formation apparatus of FIG. 7. [Figure 12] 8 is a cross-sectional view showing an example of a target film deposition module mounted in the film deposition apparatus of FIG. 7. [Figure 13] FIG. 13 is a diagram showing the results of measuring the contact angle of the surface of Samples 1 to 4 of the experimental example before and after the film formation flow of the SiO 2 film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment will be described with reference to the accompanying drawings.

[0011] <First embodiment> First, the first embodiment will be described. FIG. 1 is a flowchart showing a film forming method according to a first embodiment, and FIG. 2 is a cross-sectional view showing each process.

[0012] 2(a), a substrate W including a first film 11 having a first surface 11a and a second film 12 having a second surface 12a is prepared (step ST1). The second film 12 is a film different from the first film 11.

[0013] The first film 11 is formed on the substrate 10 and is, for example, an insulating film (dielectric film). When the first film 11 is an insulating film, a conductive film may be formed between the substrate 10 and the first film 11. The insulating film constituting the first film 11 may be an interlayer insulating film. A low dielectric constant (Low-k) film is suitable as the interlayer insulating film.

[0014] The insulating film constituting the first film 11 is not particularly limited, but examples thereof include a SiO 2 film, a SiN film, a SiOC film, a SiON film, and a SiOCN film.

[0015] The first film 11 has a recess such as a trench or a hole, and the recess is filled with the second film 12. The second film 12 is a conductive film such as a metal film. The conductive film (metal film) constituting the second film 12 is not particularly limited, but examples thereof include a Cu film, a Co film, a Ru film, a W film, and a Mo film.

[0016] The first film 11 and the second film 12 may be combined in any desired manner, but an example of such a combination is that the first film 11 is a SiO 2 film and the second film 12 is a Ru film.

[0017] For example, a semiconductor wafer having a base 10 made of silicon or a compound semiconductor can be used as the substrate W. Examples of compound semiconductors include GaAs, SiC, GaN, and InP.

[0018] A barrier film 13 may be provided between the first film 11 and the second film 12. When the first film 11 is an insulating film and the second film 12 is a metal film, the barrier film 13 has a function of suppressing diffusion of metal from the metal film to the insulating film. The barrier film 13 is not particularly limited, but examples thereof include a TaN film and a TiN film.

[0019] In the case where the substrate W has a barrier film 13, the barrier film 13 has a third surface 13a formed between the first surface 11a and the second surface 12a.

[0020] It should be noted that the substrate W is not limited to the structure shown in FIG. 2(a) as long as it has a first film having an exposed first surface and a second film having an exposed second surface.

[0021] Next, as shown in FIG. 2(b), a graphene-containing film 14 is selectively formed on the second surface 12a of the substrate W (Step ST2).

[0022] The graphene-containing film 14 is formed by covalent bonds (sp 2 The carbon material film mainly contains graphene, which is composed of an aggregate of six-membered ring structures formed by bonding between the carbon nanotubes and the graphene nanotubes, and is formed as a film that inhibits (blocks) the formation of the target film to be formed next.

[0023] The graphene-containing film 14 may be formed only of graphene, or may contain other carbon materials and amorphous components such as graphite, diamond, charcoal, carbon nanotubes, and fullerene in addition to graphene. It is sufficient that the graphene-containing film 14 is composed of at least 50% graphene, and it is preferable that the graphene-containing film 14 is composed of 90% graphene or more. In general, the attachment of graphene can be more selective on metals than on insulators. Therefore, when the second film 12 is a metal film, the graphene-containing film 14 is selectively formed on the second surface 12a of the second film 12.

[0024] The graphene-containing film 14 can be formed by a plasma CVD method. A carbon-containing gas can be used as a raw material gas for film formation. In addition to the carbon-containing gas, H2 gas or N2 gas may be added. Furthermore, a rare gas such as Ar, He, Ne, Kr, or Xe may be added as a plasma generating gas.

[0025] Examples of the carbon-containing gas include hydrocarbon gases such as ethylene (C2H4), methane (CH4), ethane (C2H6), propane (C3H8), propylene (C3H6), and acetylene (C2H2). However, the graphene-containing film 14 may be formed by a plasma ALD method.

[0026] The plasma used to form the graphene-containing film 14 is not particularly limited, and various types such as capacitively coupled plasma, inductively coupled plasma, and microwave plasma can be used. Among these, microwave plasma can be preferably used. Microwave plasma is a plasma with high radical density and low electron temperature. Therefore, the carbon-containing gas can be dissociated into a state suitable for graphene growth at a relatively low temperature, and a high-quality film can be obtained. In addition, the graphene-containing film 14 can be formed on the second film 12 without damaging the second film 12 as the base or the film being formed.

[0027] The pressure when forming the graphene-containing film 14 can be appropriately set depending on the plasma to be generated. The temperature when forming the graphene-containing film 14 may be 250 to 450° C., and is preferably 400 to 450° C. If the temperature is lower than 250° C., the effect of inhibiting the formation of the target film (blocking ability) even in the subsequent plasma treatment tends to be low, and if the temperature exceeds 450° C., there is a concern that the second film 12 may be damaged when the second film 12 is a metal film.

[0028] The thickness of the graphene-containing film 14 may be in the range of 0.5 to 10 nm, and is preferably in the range of 4 to 6 nm. If the thickness is thinner than 0.5 nm, it becomes difficult to obtain the effect of inhibiting the formation of the target film even in the next plasma treatment, and there is a concern that the second film 12 may be damaged by the next plasma treatment. On the other hand, if the thickness exceeds 10 nm, a relatively large amount of carbon nanowires, carbon nanowalls, etc. are formed, and an unintended graphene-containing film may be formed, which may result in a decrease in the effect of inhibiting the formation of the film.

[0029] Next, as shown in FIG. 2(c), the substrate W on which the graphene-containing film 14 has been formed is treated with hydrogen-containing plasma (step ST3).

[0030] The treatment with hydrogen-containing plasma is a modification treatment for enhancing the target film formation inhibitory effect of the graphene-containing film 14. The use of graphene as a target film formation inhibitor is described in the above Patent Documents 3 and 4. However, it has been found that a sufficient target film formation inhibitory effect cannot be obtained by simply forming graphene. This is thought to be because, when graphene is simply formed, defects present on the graphene surface become the starting points for nucleation of the target film, and the formation of the target film progresses from the nuclei of the generated target film.

[0031] Therefore, by treating the graphene-containing film 14 with hydrogen-containing plasma after the film is formed, defects present in the graphene of the graphene-containing film 14 are repaired (terminated). Since hydrogen has a small atomic radius, hydrogen ions and radicals can easily enter the film by generating plasma of a hydrogen-containing gas, and the defects can be repaired. That is, the hydrogen-containing plasma treatment can modify the graphene-containing film 14 into a film that has a high film formation inhibition effect on the target film, and can be turned into a modified graphene-containing film 14a.

[0032] The hydrogen-containing plasma can be formed by turning a hydrogen-containing gas into plasma. Hydrogen gas (H2 gas) can be used as the hydrogen-containing gas. In addition to H2 gas, NH3 gas, H2O gas, H2O2 gas, HF gas, etc. can be used. Hydrogen also contains deuterium, and the hydrogen-containing gas may be deuterium gas (D2 gas) or heavy water (D2O). Furthermore, in addition to these hydrogen-containing gases, an inert gas (for example, a rare gas such as Ar gas or N2 gas) may be contained. As an example, H2-Ar plasma made of H2 gas and Ar gas can be used.

[0033] The plasma used in the hydrogen-containing plasma treatment is not particularly limited, and various types can be used, such as capacitively coupled plasma, inductively coupled plasma, microwave plasma, etc. Microwave plasma has a high radical density and a low electron temperature, so it can perform treatment efficiently with little damage.

[0034] The hydrogen-containing plasma treatment in step ST3 may be performed in a different processing vessel from or in the same processing vessel as the film-forming process in step ST2 for the graphene-containing film 14. When the same plasma source is used for both processes, the hydrogen-containing plasma treatment in step ST3 may be performed in the same processing vessel as the film-forming process in step ST2 for the graphene-containing film 14.

[0035] The hydrogen-containing plasma treatment in step ST3 can be performed under the conditions of a temperature of 100 to 400° C., a power of 50 to 3000 W, and a time of 1 to 60 sec. The pressure during the hydrogen-containing plasma treatment can be appropriately set depending on the plasma to be generated.

[0036] Next, as shown in FIG. 2(d), a target film 15 is selectively formed on the first surface 11a of the substrate W (step ST4).

[0037] The target film 15 is not particularly limited, but may be a SiO2 film. The SiO2 film can be suitably formed by a process including a step of coating the first surface 11a with a metal-containing catalyst layer and a step of exposing the substrate W after coating to a process gas containing a silanol gas, as described in Patent Document 3.

[0038] The step of coating the first surface 11a of the first film 11 with a metal-containing catalyst layer can be performed by exposing the substrate W to a gas containing a metal. When the first film 11 is an insulating film and the second film 12 is a conductive film (metal film), the gas containing a metal can be selectively adsorbed on the first surface 11a, and a metal-containing catalyst layer can be selectively formed on the first surface 11a. The metal reacts to form a chemisorption layer with a thickness of less than a monolayer. Each gas pulse includes a respective purge or evacuation step to remove residual gas from the processing vessel. The modified graphene-containing film is less reactive, so that the metal-containing catalyst is less likely to be adsorbed, and a metal-containing catalyst layer is selectively formed on the first surface 11a of the first film 11, and as described below, the silanol gas selectively reacts with the metal-containing catalyst layer on the first surface 11a.

[0039] As the metal for forming the metal-containing catalyst layer, either one or both of Al and Ti can be used. As the metal-containing catalyst layer, for example, metal Al, Al2O3, AlN, Al alloy, Al-containing precursor, metal Ti, TiO2, TiN, Ti alloy, Ti-containing precursor, TiAlN, TiAlC, etc. can be mentioned. As the Al-containing precursor, various materials can be used, such as organic Al compounds such as AlMe3 (TMA). Similarly, as the Ti-containing precursor, various materials can be used, such as organic Ti compounds such as Ti(NEt2)4 (TDEAT).

[0040] As the silanol gas, for example, tris(tert-pentoxy)silanol (TPSOL), tris(tert-butoxy)silanol, bis(tert-butoxy)(isopropoxy)silanol can be used. In addition to the silanol gas, the processing gas may contain an inert gas such as Ar gas.

[0041] At this time, the thickness of the SiO2 film is controlled by the self-limiting adsorption of the silanol gas onto the metal-containing catalyst layer. The catalytic action of the metal-containing catalyst layer continues until the film thickness reaches about 3 to 5 nm. The process of coating the metal-containing catalyst layer and the process of exposing to the silanol-containing treatment gas are repeated once or multiple times to selectively form a SiO2 film of a desired thickness on the first surface 11a. This film formation can be performed at a temperature of 150°C or less, preferably 120°C or less, or even 100°C, without using plasma.

[0042] In addition, the SiO2 film may be formed by general CVD or ALD as long as selective deposition is possible.

[0043] The target film 15 may be, in addition to a SiO2 film, for example, an Al2O3 film, a SiN film, a ZrO2 film, a HfO2 film, etc. These films can also be selectively formed on the first surface 11a of the first film 11 by CVD, ALD, etc.

[0044] Next, as shown in FIG. 2(e), if necessary, excess portions of the target film 15 are removed by etching (step ST5).

[0045] For example, when the barrier film 13 is provided as in this example, the target film 15 is also formed on the third surface 13a of the barrier film 13, and the end of the target film 15 may protrude from the first surface 11a, and this protruding portion 15a becomes an excess portion. Moreover, since the target film 15 is formed thicker than the desired thickness in the film thickness direction, there is also an excess portion in the thickness direction. In step ST5, the protruding portion 15a of the target film 15 and the portion thicker than the desired thickness are removed by etching as the excess portion.

[0046] The etching at this time is not particularly limited and can be performed by various methods. For example, when the target film 15 is a SiO2 film, gas etching with HF gas and TMA gas or gas etching with HF gas and NH3 gas can be performed without plasma. Gas etching with HF gas and TMA gas can be performed by ALE, which repeats a step of supplying HF gas to the surface of the SiO2 film to fluorinate the surface and then supplying TMA gas to remove fluoride by ligand exchange. Gas etching with HF gas and NH3 gas is known as a chemical oxide removal process (COR). Specifically, HF gas and NH3 gas are adsorbed on the surface of the SiO2 film, and these are reacted with the oxide film to generate ammonium silicofluoride (AFS), which is an ammonium fluoride-based compound, and this is removed by heating.

[0047] Furthermore, regardless of the material of the target film 15, H2 plasma processing or plasma etching using a CF-based gas, which have been conventionally commonly used, can also be used.

[0048] The etching in step ST5 is not essential, and may not be performed if there is little risk of the target film 15 protruding from the first surface 11a and the thickness of the target film 15 is the desired thickness, such as in the case of forming a second film without using a barrier film or in the case of forming a graphene-containing film 14 also on the barrier film 13a.

[0049] By performing steps ST1 to ST5 as described above, the target film 15 can be selectively formed only on the first surface 11a of the first film 11.

[0050] Although the above description has been given taking the example of performing steps ST1 to ST5 in order, steps ST3 and ST4 may be repeatedly performed. This is effective in the case where the film formation inhibition effect of the graphene-containing film weakens while the target film 15 is being formed in step ST4. In this case, the conditions for performing the hydrogen-containing plasma treatment in step ST3 may be different from those in the first and second or subsequent times, or may be the same.

[0051] As described in the above Patent Documents 1 and 2 and Non-Patent Document 1, when SAM is used as a film formation inhibitor to inhibit the formation of the target film, multiple steps such as oxidation treatment and plasma treatment are included. For this reason, multiple treatments including heating are performed on the metal surface of the second film. Since the SAM itself is a molecular adsorption layer, it has a film thickness of only about 1 nm at most, so the metal film is easily damaged by multiple treatments performed on the metal surface of the second film. In addition, since the SAM has a film thickness of about 1 nm, lateral growth may not be suppressed even when the film is selectively formed. Furthermore, when the second film is a Ru film, it is difficult to inhibit film formation by the SAM.

[0052] In contrast, as described in the above Patent Documents 3 and 4, when graphene is used as a target film formation inhibitor, the film thickness can be increased to a certain extent, so that even when the second film, which is the base, is a metal layer, damage can be reduced and the lateral growth of the target film can be suppressed. However, it has been found that simply forming a graphene film does not provide a sufficient target film formation inhibition effect because defects on the graphene surface become the starting points for nucleation of the target film, making it difficult to ensure the desired selectivity.

[0053] For this reason, in this embodiment, after the graphene-containing film 14 is formed on the second surface 12a of the second film 12, a treatment is performed with a hydrogen-containing plasma. This makes it possible to repair (terminate) and modify defects present in the graphene of the graphene-containing film 14, and ensure a sufficient target film formation inhibition effect on the second film 12. For this reason, it is possible to selectively form the target film 15 on the first surface 11a of the first film 11 with higher accuracy while suppressing damage.

[0054] Moreover, a higher effect can be obtained by adjusting the film thickness and temperature when forming the graphene-containing film 14. Furthermore, by using the graphene-containing film 14 as a film-formation inhibitor, even when, for example, a SiO2 film is used as the first film 11 and a Ru film is used as the second film 12, selective film formation of the target film is possible.

[0055] <Second embodiment> Next, a second embodiment will be described. FIG. 3 is a flow chart showing a film forming method according to the second embodiment, and FIG. 4 is a cross-sectional view showing some of the steps of FIG.

[0056] In this embodiment, a pretreatment process is added to the film forming method described in the first embodiment.

[0057] 2(a) in which the second film 12 is made of metal, a native oxide film 16 may be formed on the surface of the second film 12 as shown in FIG 4(a) when the substrate W is held in the atmosphere. In such a case, the second surface 12a for forming the graphene-containing film 14 is not exposed, so that it is necessary to remove the native oxide film 16 prior to forming the graphene-containing film 14 in step ST2.

[0058] That is, in this embodiment, first, as shown in FIG. 4(a), a substrate W is prepared which includes a first film 11 having a first surface 11a and a second film 12 having a native oxide film 16 formed on its surface (step ST1').

[0059] Next, as shown in FIG. 4(b), a pretreatment is performed to reduce and remove the native oxide film 16, thereby exposing the second surface 12a of the second film 12 (step ST6).

[0060] This step ST6 can be performed by, for example, hydrogen annealing or hydrogen plasma processing. The temperature at this time can be 500° C. or less. Hydrogen plasma processing can be performed at a lower temperature than hydrogen annealing. Hydrogen annealing is performed by introducing hydrogen gas (H2 gas) into the processing vessel while heating the substrate W in the processing vessel. Hydrogen plasma processing is performed by applying hydrogen plasma to the substrate W in the processing vessel. Either of these processes may be performed using H2 gas alone, or may be performed by adding an inert gas such as Ar gas to H2 gas.

[0061] Thereafter, similarly to the first embodiment, a process of selectively forming a graphene-containing film 14 in step ST2, a process of performing a treatment with hydrogen-containing plasma in step ST3, a process of selectively forming a target film in step ST4 are performed, and an etching process in step ST5 is performed as necessary.

[0062] <Third embodiment> FIG. 5 is a flow chart showing a film forming method according to the second embodiment, and FIG. 6 is a cross-sectional view showing some of the steps of FIG.

[0063] In the third embodiment, after steps ST1 to ST5 are performed in the same manner as in the first embodiment, the graphene-containing film 14a is removed (step ST7) as shown in Fig. 6. Step ST7 is a process that is performed when necessary for device convenience.

[0064] This step ST7 can be performed by, for example, hydrogen plasma processing. The temperature at this time can be set to 500° C. or less. The hydrogen plasma processing is performed by applying hydrogen plasma to the substrate W placed in the processing chamber. The hydrogen plasma processing can be performed using H2 gas alone, or can be performed by adding an inert gas such as Ar gas to H2 gas.

[0065] <Film forming equipment> Next, a film forming apparatus for carrying out the above-described film forming method will be described. [Overall configuration] Fig. 7 is a schematic diagram showing an example of an overall configuration of a film formation apparatus capable of carrying out the film formation method according to one embodiment. The film formation apparatus 100 in Fig. 7 is a multi-chamber type apparatus capable of carrying out the film formation method according to the first embodiment, and is configured as an apparatus capable of carrying out the above steps ST2 to ST5 in situ.

[0066] 7, the film formation apparatus 100 includes a graphene-containing film formation module 200, a hydrogen-containing plasma processing module 300, a target film formation module 400, and an etching module 500. These modules are each connected to a vacuum transfer chamber 101 via a gate valve G. The inside of the vacuum transfer chamber 101 is evacuated by a vacuum pump and maintained at a predetermined vacuum level.

[0067] The graphene-containing film deposition module 200 selectively deposits a graphene-containing film on a second surface of a substrate W by plasma CVD or plasma ALD.

[0068] The hydrogen-containing plasma processing module 300 is for processing the substrate W after the graphene-containing film is formed thereon with a hydrogen-containing plasma to modify the graphene-containing film.

[0069] The target film deposition module 400 selectively forms a target film, for example, a SiO 2 film, on a first surface of the substrate W.

[0070] The etching module 500 is for etching away excess portions of the target film.

[0071] Three load lock chambers 102 are connected to the other three walls of the vacuum transfer chamber 101 via gate valves G1. An atmospheric transfer chamber 103 is provided on the opposite side of the load lock chamber 102 from the vacuum transfer chamber 101. The three load lock chambers 102 are connected to the atmospheric transfer chamber 103 via gate valves G2. The load lock chamber 102 controls pressure between atmospheric pressure and vacuum when transferring the substrate W between the atmospheric transfer chamber 103 and the vacuum transfer chamber 101.

[0072] The atmospheric transfer chamber 103 has three carrier attachment ports 105 on the wall opposite to the wall where the load lock chamber 102 is attached, for attaching carriers (FOUP, etc.) C that accommodate the substrates W. Also, an alignment chamber 104 for aligning the substrates W is provided on a side wall of the atmospheric transfer chamber 103. A downflow of clean air is formed within the atmospheric transfer chamber 103.

[0073] A first transfer mechanism 106 is provided in the vacuum transfer chamber 101. The first transfer mechanism 106 transfers a substrate W to the graphene-containing film deposition module 200, the hydrogen-containing plasma processing module 300, the target film deposition module 400, the etching module 500, and the load lock chamber 102. The first transfer mechanism 106 has two transfer arms 107a and 107b that are independently movable.

[0074] A second transfer mechanism 108 is provided in the atmospheric transfer chamber 103. The second transfer mechanism 108 transfers the substrate W to the carrier C, the load lock chamber 102, and the alignment chamber 104.

[0075] The film forming apparatus 100 has an overall control unit 110. The overall control unit 110 has a main control unit having a CPU (computer), an input device, an output device, a display device, and a storage device. The main control unit controls each component of the graphene-containing film forming module 200, the hydrogen-containing plasma processing module 300, the target film forming module 400, the etching module 500, the vacuum transfer chamber 101, and the load lock chamber 102. The main control unit of the overall control unit 110 causes the film forming apparatus 100 to perform an operation for forming a film based on a process recipe stored in, for example, a storage medium built into the storage device or a storage medium set in the storage device. Note that a lower control unit may be provided in each module, and the overall control unit 110 may be configured as a higher control unit.

[0076] In the film formation apparatus 100 configured as above, the substrate W is taken out of the carrier C connected to the atmospheric transfer chamber 103 by the second transfer mechanism 108, and is transferred into one of the load lock chambers 102 after passing through the alignment chamber 104. Then, after the inside of the load lock chamber 102 is evacuated to a vacuum, the substrate W is transferred by the first transfer mechanism 106 to the graphene-containing film formation module 200, the hydrogen-containing plasma treatment module 300, the target film formation module 400, and the etching module 500, where the processes of steps ST2 to ST5 are performed.

[0077] After the above processing is completed, the substrate W is transported to one of the load lock chambers 102 by the first transport mechanism 106, and the substrate W in the load lock chamber 102 is returned to the carrier C by the second transport mechanism 108.

[0078] The above-mentioned processing is performed continuously and simultaneously in parallel on a plurality of substrates W until the film formation processing on a predetermined number of substrates W is completed.

[0079] In the film forming apparatus 100, the processes of steps ST2 to ST5 are performed in separate single-wafer modules, so that it is easy to set the optimum temperature for each process, and since the series of processes can be performed without breaking the vacuum, oxidation during the process can be suppressed.

[0080] In the above-described film formation apparatus 100, steps ST2 to ST5 are performed in separate modules, but at least some of the steps may be performed in the same module. When performing the pretreatment step of step ST6 and the graphene-containing film removal step of step ST7, the size of the vacuum transfer chamber 101 may be changed to connect a pretreatment module and a graphene-containing film removal module to the vacuum transfer chamber 101, or these processes may be performed in other modules. Furthermore, the film formation apparatus is not limited to the form shown in FIG. 7, and the connection form of each module to the vacuum transfer chamber may be arbitrary, and the form is not limited to the connection of each module to the vacuum transfer chamber, and the substrate may be serially transferred to each module.

[0081] [Example of graphene-containing film deposition module] Next, an example of a graphene-containing film formation module will be described. FIG. 8 is a cross-sectional view that illustrates an example of a graphene-containing film formation module, FIG. 9 is a cross-sectional view that illustrates a microwave radiation mechanism in the graphene-containing film formation module of FIG. 8, and FIG. 10 is a bottom view that illustrates a ceiling wall portion of a processing vessel in the graphene-containing film formation module of FIG. 8.

[0082] The graphene-containing film deposition module 200 is configured as a microwave plasma processing apparatus, and includes a processing vessel 201, a mounting table 202, a gas supply unit 203, an exhaust unit 204, and a microwave introduction unit 205.

[0083] The processing vessel 201 accommodates the substrate W, and is made of a metal material such as aluminum (Al) or an alloy thereof, has a substantially cylindrical shape, and includes a plate-like top wall portion 211, a bottom wall portion 213, and a side wall portion 212 connecting them. The inner surfaces of the top wall portion 211 and the side wall portion 212 form the inner wall of the processing vessel 201. The inner wall surface of the processing vessel 201 may be coated with Al2O3, Y2O3, or the like.

[0084] The microwave introducing device 205 is provided at the top of the processing vessel 201, and functions as a plasma generating means for generating plasma by introducing electromagnetic waves (microwaves) into the processing vessel 201. The microwave introducing device 205 will be described in detail later.

[0085] The ceiling wall 211 has a plurality of openings into which a microwave radiation mechanism and a gas introduction unit of the microwave introduction device 205, which will be described later, are fitted. The side wall 212 has a loading / unloading port 214 for loading / unloading the substrate W between the processing vessel 201 and the vacuum transfer chamber 101 adjacent thereto. The loading / unloading port 214 is adapted to be opened and closed by a gate valve G. The bottom wall 213 is provided with an exhaust device 204. The exhaust device 204 is provided on an exhaust pipe 216 connected to the bottom wall 213, and includes a vacuum pump and a pressure control valve. The inside of the processing vessel 201 is exhausted through the exhaust pipe 216 by the vacuum pump of the exhaust device 204. The pressure inside the processing vessel 201 is controlled by a pressure control valve.

[0086] The mounting table 202 is disposed inside the processing vessel 201, and the substrate W is mounted thereon. The mounting table 202 is disk-shaped and made of ceramics such as AlN. The mounting table 202 is supported by a cylindrical support member 220 made of ceramics such as AlN, which extends upward from the center of the bottom of the processing vessel 201. A guide ring 281 for guiding the substrate W is provided on the outer edge of the mounting table 202. Furthermore, inside the mounting table 202, lifting pins (not shown) for lifting and lowering the substrate W are provided so as to be protrudible and retractable from the upper surface of the mounting table 202. Furthermore, a resistance heating type heater 282 is embedded inside the mounting table 202, and this heater 282 heats the substrate W thereon via the mounting table 202 by receiving power from a heater power source 283. Furthermore, a thermocouple (not shown) is inserted into the mounting table 202, and the heating temperature of the substrate W can be controlled based on a signal from the thermocouple. Furthermore, an electrode 284 having a size approximately equal to that of the substrate W is embedded above the heater 282 in the mounting table 202, and a high frequency bias power supply 222 is electrically connected to this electrode 284. A high frequency bias for attracting ions is applied from this high frequency bias power supply 222 to the mounting table 202. Note that the high frequency bias power supply 222 may not be provided depending on the characteristics of the plasma processing.

[0087] The gas supply unit 203 is for supplying a plasma generating gas (a rare gas such as Ar gas), a carbon-containing gas for forming a graphene film (e.g., a hydrocarbon gas such as ethylene (C2H4), methane (CH4), ethane (C2H6), propane (C3H8), propylene (C3H6), or acetylene (C2H2)) into the processing vessel 201. In addition, H2 gas or N2 gas may be supplied. The gas supply unit 203 includes a gas supply mechanism 292 having a plurality of gas supply sources for supplying these gases, pipes connected to the respective gas supply sources, and valves and flow rate controllers provided on the pipes. The gas supply unit 203 further includes a common pipe 291 for introducing gas from the gas supply mechanism 292, and a plurality of gas introduction nozzles 223 connected to the pipe 291. The gas introduction nozzle 223 is fitted into an opening formed in the ceiling wall 211 of the processing vessel 201, and gas from the gas supply mechanism 292 is introduced into the processing vessel 201 through the piping 291 and the gas introduction nozzle 223. Note that dissociation of the gas may be adjusted by adjusting the distance from the substrate W to the gas introduction position by an appropriate means.

[0088] As described above, the microwave introduction device 205 is provided above the processing vessel 201, and functions as a plasma generating means for generating plasma by introducing electromagnetic waves (microwaves) into the processing vessel 201. As shown in FIG. 8, the microwave introduction device 205 has a top wall portion 211 that functions as a top plate, a microwave output unit 230, and an antenna unit 240.

[0089] The microwave output unit 230 generates microwaves and distributes and outputs the microwaves to a plurality of paths, and includes a microwave power source, a microwave oscillator, an amplifier, and a distributor. The microwave oscillator is solid-state, and oscillates (e.g., PLL oscillates) microwaves at, for example, 860 MHz. The microwave frequency is not limited to 860 MHz, and frequencies in the range of 700 MHz to 10 GHz, such as 2.45 GHz, 8.35 GHz, 5.8 GHz, and 1.98 GHz, can be used. The microwaves oscillated by the microwave oscillator are amplified by the amplifier and distributed to a plurality of paths by the distributor. The distributor distributes the microwaves while matching the impedances of the input side and output side.

[0090] The antenna unit 240 introduces the microwaves output from the microwave output unit 230 into the processing vessel 201. The antenna unit 240 includes a plurality of antenna modules 241. Each of the plurality of antenna modules 241 introduces the microwaves distributed by the distributor into the processing vessel 201. The plurality of antenna modules 241 each have an amplifier unit 242 that mainly amplifies and outputs the distributed microwaves, and a microwave radiation mechanism 243 that radiates the microwaves output from the amplifier unit 242 into the processing vessel 201.

[0091] The amplifier section 242 has a phase shifter, a variable gain amplifier, a main amplifier, and an isolator, which are arranged in this order from the upstream side. The phase of the microwave is adjusted by the phase shifter, and the power level of the microwave is adjusted by the variable gain amplifier, after which the microwave is amplified by the main amplifier. The main amplifier is configured as a solid-state amplifier. The isolator separates the reflected microwave that is reflected by the antenna section of the microwave radiation mechanism 243 (described later) and heads toward the main amplifier.

[0092] As shown in Fig. 8, a plurality of microwave radiation mechanisms 243 are provided on the top wall portion 211. Moreover, as shown in Fig. 9, the microwave radiation mechanism 243 has a coaxial tube 251, a power feeding unit 255, a tuner 254, and an antenna unit 256. The coaxial tube 251 has a cylindrical outer conductor 252 and an inner conductor 253 provided coaxially with the outer conductor 252 within the outer conductor 252, and has a microwave transmission line therebetween.

[0093] The power feeding unit 255 feeds the amplified microwaves from the amplifier unit 242 to the microwave transmission line. The microwaves amplified by the amplifier unit 242 are introduced into the power feeding unit 255 from the side of the upper end of the outer conductor 252 via a coaxial cable. Microwave power is fed to the microwave transmission line between the outer conductor 252 and the inner conductor 253, and the microwave power propagates toward the antenna unit 256.

[0094] The antenna unit 256 radiates microwaves from the coaxial tube 251 into the processing vessel 201, and is provided at the lower end of the coaxial tube 251. The antenna unit 256 has a disk-shaped planar antenna 261 connected to the lower end of the inner conductor 253, a slow-wave material 262 arranged on the upper surface side of the planar antenna 261, and a microwave transmission plate 263 arranged on the lower surface side of the planar antenna 261. The microwave transmission plate 263 is fitted into the top wall 211, and its lower surface is exposed to the internal space of the processing vessel 201. The planar antenna 261 has a slot 261a formed to penetrate through it. The shape of the slot 261a is appropriately set so that the microwaves are efficiently radiated. A dielectric may be inserted into the slot 261a. The slow-wave material 262 is formed of a material having a dielectric constant larger than that of a vacuum, and the phase of the microwaves can be adjusted by its thickness, so that the radiation energy of the microwaves can be maximized. The microwave transmitting plate 263 is also made of a dielectric material and has a shape that allows efficient radiation of microwaves in TE mode. The microwaves transmitted through the microwave transmitting plate 263 generate plasma in the space within the processing vessel 201. Examples of materials that can be used to form the slow-wave member 262 and the microwave transmitting plate 263 include quartz, ceramics, fluorine-based resins such as polytetrafluoroethylene resin, and polyimide resins.

[0095] The tuner 254 matches the impedance of the load to the characteristic impedance of the microwave power source in the microwave output unit 230. The tuner 254 constitutes a slug tuner. For example, as shown in Fig. 9, the tuner 254 has two slugs 271a and 271b, an actuator 272 that drives these two slugs independently, and a tuner controller 273 that controls the actuator 272. The slugs 271a and 271b are disposed on the base end side (upper end side) of the antenna unit 256 of the coaxial tube 251.

[0096] The slugs 271a and 271b are plate-shaped and annular, made of a dielectric material such as ceramics, and disposed between the outer conductor 252 and the inner conductor 253 of the coaxial tube 251. The actuator 272 may have, for example, two screws provided inside the inner conductor 253, into which the slugs 271a and 271b are screwed, and a motor for rotating these screws. For example, the motor rotates the screws to drive the slugs 271a and 271b individually. The actuator 272 moves the slugs 271a and 271b up and down based on a command from the tuner controller 273, and adjusts the positions of the slugs 271a and 271b so that the impedance of the termination is 50Ω.

[0097] The main amplifier of the amplifier section 242, the tuner 254, and the planar antenna 261 are arranged in close proximity to each other. The tuner 254 and the planar antenna 261 form a lumped constant circuit and function as a resonator. Although there is an impedance mismatch at the attachment portion of the planar antenna 261, the tuner 254 directly tunes the plasma load, so that tuning including the plasma can be performed with high accuracy. Therefore, the influence of reflection at the planar antenna 261 can be eliminated.

[0098] As shown in Fig. 10, in this example, seven microwave radiation mechanisms 243 are provided, and the corresponding microwave transmission plates 263 are evenly arranged in a hexagonal close-packed arrangement. That is, one of the seven microwave transmission plates 263 is arranged in the center of the top wall portion 211, and the other six microwave transmission plates 263 are arranged around it. These seven microwave transmission plates 263 are arranged so that adjacent microwave transmission plates are equally spaced apart. In addition, the multiple nozzles 223 of the gas supply mechanism 203 are arranged so as to surround the periphery of the central microwave transmission plate. The number of microwave radiation mechanisms 243 is not limited to seven.

[0099] When forming a graphene-containing film by the graphene-containing film formation module 200 configured as above, first, the substrate W is carried into the processing chamber 201 and placed on the mounting table 202.

[0100] Next, after the temperature of the substrate W is stabilized, the pressure inside the processing chamber 201 is controlled, and a graphene-containing film is formed by, for example, microwave plasma CVD.

[0101] Specifically, Ar gas, which is a plasma generating gas, is supplied from the gas introduction nozzle 223 to directly below the ceiling wall 211 of the processing vessel 201. At the same time, microwaves distributed and output from the microwave output unit 230 of the microwave introduction device 205 are radiated into the processing vessel 201 via the multiple antenna modules 241 of the antenna unit 240 to ignite plasma.

[0102] In each antenna module 241, the microwave is individually amplified by the main amplifier of the amplifier section 242, and is fed to each microwave radiation mechanism 243. The microwave fed to the microwave radiation mechanism 243 is transmitted through the coaxial tube 251 to reach the antenna section 256. At this time, the microwave is automatically matched in impedance by the slugs 271a and 271b of the tuner 254, and is radiated from the slot 261a of the planar antenna 261 through the slow-wave material 262 of the antenna section 256 from the tuner 254 in a state where there is substantially no power reflection. The microwave then further passes through the microwave transmitting plate 263, and is transmitted through the surface (lower surface) of the microwave transmitting plate 263 in contact with the plasma to form a surface wave, and a surface wave plasma by Ar gas is generated in the area directly below the top wall section 211.

[0103] At the timing when the plasma is ignited, a carbon-containing gas, such as C2H4 gas, which is a film-forming raw material gas, is supplied from the gas supply nozzle 223. At this time, N2 gas or H2 gas may be supplied as necessary.

[0104] These gases are excited by the plasma and dissociated, and are supplied to the substrate W placed on the mounting table 202. The substrate W is disposed in a region away from the plasma generation region, and the plasma diffused from the plasma generation region is supplied to the substrate W, so that the plasma on the substrate W has a low electron temperature and is low-damage, and is a high-density plasma mainly composed of radicals. This allows nucleation and lateral growth to proceed smoothly, and graphene crystals with fewer defects grow. As a result, a graphene-containing film with good film quality is formed, which may become a film that inhibits the formation of a target film.

[0105] From the viewpoint of using the graphene-containing film as a film that inhibits the formation of a target film, the substrate temperature during the formation of the graphene-containing film may be 250 to 450° C., and the film thickness may be 0.5 to 10 nm.

[0106] In this example, the carbon-containing gas C2H4 gas is supplied to the plasma generating region and dissociated, but dissociation may be suppressed by dissociating the carbon-containing gas with plasma diffused from the plasma generating region by appropriate means. Also, a carbon-containing gas such as C2H4 gas may be supplied to the plasma generating region and directly ignited with plasma without using Ar gas as the plasma generating gas.

[0107] In the graphene-containing film deposition module 200 of this example, the microwaves distributed to multiple sources are individually amplified by the amplifier unit 242 and individually radiated from the microwave radiation mechanism 243 to generate microwave plasma, so that a large isolator or a combiner is not required, and the module is compact. Furthermore, since the tuner 254 can tune the plasma with high precision at the planar slot antenna mounting portion where impedance mismatch exists, the influence of reflection can be reliably eliminated and high-precision plasma control is possible. In addition, by providing multiple microwave transmission plates 263 in this way, the total area of ​​the microwave transmission region can be made smaller than that of a microwave plasma source having a single microwave transmission path and microwave transmission plate. This makes it possible to reduce the microwave power required for stable ignition and discharge of plasma.

[0108] The graphene-containing film deposition module is not limited to a microwave plasma processing apparatus as in this example, and may be one that uses other plasmas, such as a capacitively coupled plasma processing apparatus or an inductively coupled plasma processing apparatus.

[0109] [Example of a hydrogen-containing plasma processing module] Next, an example of a hydrogen-containing plasma processing module will be described. 11 is a cross-sectional view showing an example of a hydrogen-containing plasma processing module. The hydrogen-containing plasma processing module 300 has a metallic processing vessel 301 having a substantially cylindrical shape. An exhaust pipe 311 is connected to the bottom of the processing vessel 301, and the exhaust pipe 311 is provided with an exhaust mechanism 312 having an automatic pressure control valve for controlling the pressure inside the processing vessel 301 and a vacuum pump for exhausting the inside of the processing vessel 301. The exhaust mechanism 312 makes it possible to evacuate the inside of the processing vessel 301 and control the pressure to a desired level.

[0110] A side wall of the processing vessel 301 is provided with a loading / unloading port 313 for loading / unloading the substrate W between the processing vessel 301 and the vacuum transfer chamber 101 provided adjacent thereto, and a gate valve G for opening and closing this loading / unloading port 313.

[0111] A mounting table 302 for horizontally supporting a substrate W is provided in the processing vessel 301. The mounting table 302 is supported at the center of the bottom wall of the processing vessel 301 via a support member 303.

[0112] The mounting table 302 is grounded via the processing vessel 301 and functions as a lower electrode. The mounting table 302 may be made of metal or ceramics, and if it is made of ceramics, an electrode plate is provided therein. A heater 318 for heating the substrate W is provided inside the mounting table 302. The mounting table 302 is provided with a plurality of lifting pins (not shown) for supporting and lifting the substrate W, which can be protruded and retracted from the surface of the mounting table 302.

[0113] A circular hole is formed in the ceiling wall 301a of the processing vessel 301, and a disk-shaped shower head 320 functioning as an upper electrode is fitted in the hole via an insulating member 326. The shower head 320 has a base member 321 and a shower plate 322. A gas diffusion space 323 is formed between the base member 321 and the shower plate 322. A plurality of gas discharge holes 324 are formed in the shower plate 322, which penetrate from the gas diffusion space 323 to the inside of the processing vessel 301. A gas introduction hole 325 is formed in the center of the base member 321 so as to penetrate into the gas diffusion space 323. A pipe 331 extending from a gas supply unit 330 is connected to the gas introduction hole 325, and a gas from the gas supply unit 330 is discharged into the processing vessel 301 through the shower head 320.

[0114] The gas supply unit 330 supplies a hydrogen-containing gas such as H2 gas. In addition to the hydrogen-containing gas, a rare gas such as Ar gas or an inert gas such as N2 gas may be supplied. As the hydrogen-containing gas, NH3 gas, H2O gas, H2O2 gas, HF gas, etc. can be used in addition to H2 gas.

[0115] A high-frequency power supply 316 is connected to the shower head 320, which functions as an upper electrode, via a power supply line 317. A matching box 315 is connected to the middle of the power supply line 317. When high-frequency power is applied from the high-frequency power supply 316 to the shower head 320, a high-frequency electric field is formed between the shower head 320 and the mounting table 302. Then, the hydrogen-containing gas supplied from the gas supply unit 330 is excited by the high-frequency electric field, and hydrogen-containing plasma is generated.

[0116] In the hydrogen-containing plasma processing module configured in this manner, first, the substrate W having the graphene-containing film formed thereon is carried into the processing chamber 301 and placed on the mounting table 302.

[0117] Next, after stabilizing the temperature of the substrate W, the pressure inside the processing vessel 301 is controlled, and a hydrogen-containing gas such as H2 gas, and an inert gas as necessary, are supplied from the gas supply unit 330 into the processing vessel 301 via the shower head 320. Then, while the gas is being supplied, high-frequency power is applied from the high-frequency power supply 316 to the shower head 320, generating a hydrogen-containing plasma between the shower head 320 and the mounting table 302. Thus, the substrate W is subjected to a hydrogen-containing plasma process.

[0118] By the treatment with this hydrogen-containing plasma, the graphene-containing film formed on the substrate W can be modified into a film that has a high effect of inhibiting the formation of a target film.

[0119] In this example, the hydrogen-containing plasma is generated by capacitively coupling plasma, but other plasmas such as inductively coupling plasma and microwave plasma may be used. Microwave plasma has a high radical density and a low electron temperature, and therefore can perform efficient processing with little damage. In the case of microwave plasma, a module having the same configuration as the graphene-containing film deposition module 200 described above can be used. In addition, when microwave plasma is used, the graphene-containing film deposition module 200 may be provided with the function of the hydrogen-containing plasma processing module 300, and after the graphene-containing film is formed, the hydrogen-containing plasma processing may be performed continuously in the same processing vessel.

[0120] [Examples of applicable film deposition modules] Next, an example of a target film deposition module will be described. 12 is a cross-sectional view showing a schematic example of a target film deposition module. This target film deposition module 400 has an airtight, substantially cylindrical processing vessel 401, in which a mounting table 402 for horizontally mounting a substrate W is disposed and supported by a cylindrical support member 403 provided in the center of the bottom wall of the processing vessel 401. The mounting table 402 is provided with a heater 405 for heating the substrate W. The mounting table 402 is provided with a plurality of lift pins (not shown) for supporting and lifting the substrate W, which can be protruded and retracted from the surface of the mounting table 402.

[0121] A shower head 410 for introducing a processing gas for forming a target film into the processing vessel 401 in a shower-like manner is provided on the ceiling wall of the processing vessel 401 so as to face the mounting table 402. The shower head 410 is for discharging a gas supplied from a gas supply unit 430 (described later) into the processing vessel 401, and has a gas inlet 411 for introducing the gas formed on the upper portion. A gas diffusion space 412 is formed inside the shower head 410, and a number of gas discharge holes 413 communicating with the gas diffusion space 412 are formed on the bottom surface of the shower head 410.

[0122] An exhaust chamber 421 protruding downward is provided on the bottom wall of the processing vessel 401. An exhaust pipe 422 is connected to the side of the exhaust chamber 421, and an exhaust device 423 having a vacuum pump, a pressure control valve, etc. is connected to the exhaust pipe 422. By operating the exhaust device 423, the inside of the processing vessel 401 can be made into a predetermined reduced pressure (vacuum) state.

[0123] A transfer port 427 for transferring the substrate W between the processing vessel 401 and the vacuum transfer chamber 101 is provided on a side wall of the processing vessel 401 . The transfer port 427 is adapted to be opened and closed by a gate valve G.

[0124] The gas supply unit 430 supplies gases necessary for forming the target film. When the target film is a SiO2 film, for example, a gas containing a metal for forming a metal-containing catalyst layer and a processing gas containing silanol are supplied. In addition to silanol, an inert gas such as Ar gas may be supplied as the processing gas. As the metal for forming the metal-containing catalyst layer, either one or both of Al and Ti can be used. As the gas containing metal, an organic Al compound such as AlMe3 (TMA) can be used as an Al precursor. A pipe 435 extends from the gas supply unit 430 and is connected to the gas inlet 411.

[0125] In the target film formation module 400 configured as above, the gate valve G is opened, the substrate W is loaded into the processing vessel 401 through the load / unload port 427, and then loaded onto the mounting table 402. The mounting table 402 is heated to a predetermined temperature by the heater 405, and the substrate W loaded onto the mounting table 402 is heated to that temperature. Then, the inside of the processing vessel 401 is evacuated by the vacuum pump of the exhaust device 423, and the pressure inside the processing vessel 401 is adjusted to a predetermined pressure.

[0126] Next, for example, TMA gas is supplied from the gas supply unit 430 as a gas containing metal, and a metal-containing catalyst layer is selectively formed on the first surface of the substrate W. Then, a process gas containing silanol is supplied onto the metal-containing catalyst layer. The process of coating the metal-containing catalyst layer and the process gas supplying the silanol-containing process gas are repeated once or multiple times to selectively form a SiO2 film of a desired thickness on the first surface of the substrate W. This film formation can be performed at a temperature of 150° C. or less, preferably 120° C. or less, or even 100° C., without using plasma.

[0127] The target film may be formed by CVD or ALD, and in that case, a module having a similar configuration to the target film forming module 400 can be used.

[0128] [Example of an etching module] As described above, the etching module 500 is for removing excess portions of the target film formed on the first surface of the substrate W, and when the target film 15 is a SiO2 film, the etching can be performed without plasma by gas etching using HF gas and TMA gas, or gas etching using HF gas and NH3 gas. In this case, a module having a configuration similar to that of the target film forming module 400 described above can be used.

[0129] Also, the etching may be performed by H2 plasma processing or plasma etching using CF-based gas, which have been conventionally performed, and in this case, a module capable of generating plasma having a configuration similar to that of the above-mentioned hydrogen-containing plasma processing module 300 may be used. In this case, the high frequency power may be configured to be applied to the mounting table.

[0130] As described above, step ST5 does not have to be performed, and if step ST5 is not performed, the etching module 500 is not necessary.

[0131] The above-described film forming apparatus 100 can perform the film forming method of the first embodiment, but when performing the second or third embodiment, a film forming apparatus is used that further includes at least one of a module for performing the pretreatment in step ST6 and a module for performing the graphene-containing film removal treatment in step ST7. The pretreatment module and the graphene-containing film removal module can be performed by a module equipped with a plasma generation mechanism similar to the hydrogen-containing plasma treatment module 300. Moreover, the hydrogen-containing plasma treatment module 300 can be configured to have the functions of at least one of these modules.

[0132] <Experimental Example> Next, an experimental example will be described. Here, a graphene-containing film was formed as a film-formation inhibitor that inhibits the formation of a target film on a Ru film, and its effectiveness was verified.

[0133] The target film was a SiO2 film. The film formation inhibition (blocking ability) was evaluated by the contact angle of the film surface. The larger the contact angle, the lower the surface activity and the higher the film formation inhibition (blocking ability).

[0134] The graphene-containing films were formed to thicknesses of about 2 nm and about 4 nm using a module configured as a microwave plasma processing apparatus shown in Figs. 8 to 10, using C2H4 gas as a carbon-containing gas, setting the substrate temperature to 400°C, and forming the films to thicknesses of about 2 nm and about 4 nm (Samples 1 and 2). For the 4 nm film thickness, a hydrogen-containing plasma treatment was performed (Sample 3). The hydrogen-containing plasma treatment was performed using the module shown in Fig. 11, supplying H2 gas and Ar gas, setting the substrate temperature to 150°C, the microwave power to 200 W, and the time to 10 sec. After forming the 4 nm film, for comparison, an H2 gas flow was performed at 150°C without using plasma (Sample 4).

[0135] A film formation flow for the target SiO2 film was carried out for these samples 1 to 4. The film formation flow was such that TMA gas was supplied, and then silanol gas was supplied.

[0136] The contact angles of the surfaces of Samples 1 to 4 were measured before and after the SiO2 film formation flow. The results are shown in FIG. 13. As shown in FIG. 13, before the SiO2 film formation flow, Samples 1 to 4 all had relatively high contact angles of about 60 to 70°, and the thicker the film, the higher the contact angle, although only slightly, and the hydrogen-containing plasma treatment tended to increase the contact angle. On the other hand, after the SiO2 film formation flow, Samples 1 and 2 in which the graphene-containing film was still formed, and Sample 4 in which the H2 gas flow was performed, all had contact angles that were reduced to about 30° or less. In contrast, Sample 3, which was subjected to the hydrogen-containing plasma treatment after the graphene-containing film was formed, maintained a contact angle of 60° or more even after the SiO2 film formation flow, and it was confirmed that the effect of inhibiting the formation of the SiO2 film was high.

[0137] <Other applications> Although the embodiments have been described above, the embodiments disclosed herein should be considered to be illustrative and not restrictive in all respects. The above-described embodiments may be omitted, substituted, or modified in various forms without departing from the scope and spirit of the appended claims.

[0138] For example, in the above embodiment, the substrate in which the second film is embedded in the recess formed in the first film is described as an example, but the arrangement of the first film and the second film is not limited to this. In addition, in a substrate having a first film and a second film different from the first film, the materials of the first film and the second film are not important as long as a graphene-containing film can be formed on a first surface of the first film and a target film can be selectively formed on a second surface of the second film.

[0139] In the above embodiment, a semiconductor wafer is used as the substrate, but the present invention is not limited to this and other substrates such as a glass substrate or a ceramic substrate may be used. [Explanation of symbols]

[0140] 10;Base 11; First membrane 11a; First surface 12; Second membrane 12a; Second surface 13. Barrier membrane 13a; Third Surface 14; Graphene-containing film 15;Target membrane 15a; protruding part 16:Natural oxide film 100; Film deposition equipment 101: Vacuum transfer chamber 102; Load lock chamber 106: First conveying mechanism 200;Graphene-containing film deposition module 300; Hydrogen-containing plasma processing module 400; Target film deposition module 500; Etching module W; Substrate

Claims

1. A method of manufacturing a substrate comprising: providing a substrate including a first film having a first surface; and a second film having a second surface, the second film being different from the first film; Selectively forming a graphene-containing film on the second surface; treating the substrate after forming the graphene-containing film with a hydrogen-containing plasma; Selectively forming a target film on the first surface; The film forming method includes the steps of:

2. The film forming method according to claim 1 , wherein the first film is an insulating film and the second film is a conductive film.

3. The first film is made of SiO ２ 3. The film forming method according to claim 2, wherein the film is at least one selected from the group consisting of a silicon nitride film, a silicon oxynitride film, a silicon oxynitride film, a silicon oxynitride film, and a silicon oxynitride film.

4. 3. The film forming method according to claim 2, wherein the second film is at least one selected from the group consisting of a Cu film, a Co film, a Ru film, a W film, and a Mo film.

5. The target film is SiO ２ Membrane, Al ２ O ３ film, SiN film, ZrO ２ membrane, HfO ２ The film forming method according to claim 1 , wherein the film is at least one selected from the group consisting of a metal oxide film and a metal oxide film.

6. The target film is SiO ２ 6. The method of claim 5, wherein selectively forming the target film comprises exposing the substrate to a gas containing a metal to coat the substrate with a metal-containing catalyst layer, and exposing the substrate after coating to a process gas containing a silanol gas.

7. The film forming method according to claim 1 , wherein the graphene-containing film is formed by plasma CVD or plasma ALD.

8. The film forming method according to claim 7 , wherein the plasma CVD or the plasma ALD is performed using microwave plasma.

9. The film forming method according to claim 7, wherein the graphene-containing film is formed at a temperature of 250 to 450° C.

10. The film forming method according to claim 9, wherein the graphene-containing film is formed at a temperature of 400 to 450° C.

11. The method according to claim 7, wherein the graphene-containing film has a thickness of 0.5 to 10 nm.

12. The method of claim 11, wherein the graphene-containing film has a thickness of 4 to 6 nm.

13. The film forming method according to claim 1 , wherein the treatment with the hydrogen-containing plasma is a treatment for modifying the graphene-containing film.

14. The treatment with the hydrogen-containing plasma is carried out using H ２ The film forming method according to claim 13 , wherein a gas is used.

15. 14. The film forming method according to claim 13, wherein the treatment with the hydrogen-containing plasma is performed at a temperature in the range of 100 to 400° C., with a power in the range of 50 to 3000 W, for a time in the range of 1 to 60 sec.

16. The method of forming a film according to claim 1 , further comprising etching away excess portions of the target film.

17. 17. The film forming method of claim 16, wherein the substrate has a barrier film between the first film and the second film, an overhanging portion of the target film is formed on a surface of the barrier film, and etching away the excess portion of the target film removes the overhanging portion as the excess portion.

18. The method of claim 1 , further comprising removing the graphene-containing film after forming the target film.

19. 7. The method of claim 1, further comprising: performing a pretreatment to remove a native oxide film formed on the second surface of the substrate before forming the graphene-containing film.

20. a graphene-containing film forming unit that forms a graphene-containing film; a hydrogen-containing plasma processing unit for performing a process using hydrogen-containing plasma; a target film forming unit that forms a target film; A control unit; having The control unit is A substrate having a first film having a first surface and a second film having a second surface and different from the first film, controlling a graphene-containing film forming unit so that a graphene-containing film is selectively formed on the second surface; controlling the hydrogen-containing plasma treatment unit so that the substrate after the graphene-containing film is formed thereon is treated with hydrogen-containing plasma; a film forming apparatus that controls the target film forming unit so that a target film is selectively formed on the first surface;

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