Film deposition method and film deposition apparatus
The method improves blocking performance and prevents substrate degradation by using fluorine-free SAMs with selective film formation and etching, addressing the limitations of fluorine-containing SAMs in existing technologies.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- TOKYO ELECTRON LTD
- Filing Date
- 2022-03-25
- Publication Date
- 2026-06-23
AI Technical Summary
Existing film forming methods using self-assembled monolayers (SAMs) containing fluorine face challenges in improving blocking performance while minimizing substrate degradation and require fluorine-free alternatives.
A film formation method involving the use of a fluorine-free organic compound to form a self-assembled monolayer, followed by fluorination and etching, to create a protective film that prevents target film formation on certain substrate regions, using TMA gas for etching and ALD for film deposition.
Enhances blocking performance and prevents substrate degradation by selectively forming films on specific substrate areas, improving film quality and reducing residual contaminants.
Smart Images
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Abstract
Description
Technical Field
[0001] The present disclosure relates to a film forming method and a film forming apparatus.
Background Art
[0002] Patent Document 1 describes a film forming method in which a target film (third film) is formed on a part of a substrate surface while inhibiting the formation of the target film (third film) on another part of the substrate surface using a self-assembled monolayer (SAM). In Patent Document 1, an organic compound containing fluorine is used as a precursor of SAM. After the formation of the target film, by irradiating at least one of ions and active species, SAM is excited and an active species having fluorine and carbon is generated. Then, the active species having fluorine and carbon reacts with the side portion of the target film adjacent to SAM. As a result, the side portion of the target film becomes a volatile compound and is removed.
Prior Art Documents
Patent Documents
[0003]
Patent Document 1
Summary of the Invention
Problems to be Solved by the Invention
[0004] One aspect of the present disclosure provides a technique for improving the blocking performance of a SAM not containing fluorine and suppressing deterioration of the substrate when improving the blocking performance.
Means for Solving the Problems
[0005] A film formation method according to one aspect of the present disclosure includes the following (A) to (F): (A) A substrate is prepared having a first film and a second film formed of a different material from the first film in different regions of its surface. (B) A self-assembled monolayer is selectively formed on the surface of the second film and on the surface of the first film using a fluorine-free organic compound. (C) After (B), the protective film is formed on the surface of the first film using the self-assembled monolayer while inhibiting the formation of the protective film on the surface of the second film. (D) After (C), the self-assembled monolayer and the protective film are fluorinated. (E) After (D), the fluorinated portion of the protective film is fluorinated. Etching gas Etching is performed. (F) After (E), the target film is formed on the surface of the protective film or the surface of the first film, while inhibiting the formation of the target film on the surface of the second film using the fluorinated self-assembled monolayer. The protective film is an AlO film, and the etching gas is TMA gas. [Effects of the Invention]
[0006] According to one aspect of this disclosure, it is possible to improve the blocking performance of a fluorine-free SAM and suppress the degradation of the substrate when improving the blocking performance. [Brief explanation of the drawing]
[0007] [Figure 1] Figure 1 is a flowchart showing a film deposition method according to one embodiment. [Figure 2] Figure 2(A) shows the first example of step S101, Figure 2(B) shows the first example of step S102, Figure 2(C) shows the first example of step S103, and Figure 2(D) shows the first example of step S104. [Figure 3] Figure 3(A) shows the first example of step S105, Figure 3(B) shows the first example of step S106, Figure 3(C) shows the first example of step S107, and Figure 3(D) shows the first example of step S109. [Figure 4]Figure 4(A) shows a first example of step S110, and Figure 4(B) shows a modified example of Figure 4(A). [Figure 5] Figure 5 is a flowchart showing an example of the subroutine for step S105. [Figure 6] Figure 6 is a flowchart showing an example of the subroutine in step S109. [Figure 7] Figure 7 is a flowchart of an example of the subroutine in step S110. [Figure 8] Figure 8 is a flowchart showing an example of the process that follows step S110 in Figure 1. [Figure 9] Figure 9(A) shows a second example of step S101, Figure 9(B) shows a second example of step S102, Figure 9(C) shows a second example of step S103, and Figure 9(D) shows a second example of step S104. [Figure 10] Figure 10(A) shows a second example of step S105, Figure 10(B) shows a second example of step S106, Figure 10(C) shows a second example of step S107, and Figure 10(D) shows a second example of step S109. [Figure 11] Figure 11(A) shows a second example of step S110, and Figure 11(B) shows a modified example of Figure 11(A). [Figure 12] Figure 12(A) shows a third example of step S101, Figure 12(B) shows a third example of step S102, Figure 12(C) shows a third example of step S103, and Figure 12(D) shows a third example of step S104. [Figure 13] Figure 13(A) shows a third example of step S105, Figure 13(B) shows a third example of step S106, Figure 13(C) shows a third example of step S107, and Figure 13(D) shows a third example of step S109. [Figure 14] Figure 14(A) shows a third example of step S110, and Figure 14(B) shows a modified example of Figure 14(A). [Figure 15] FIG. 15 is a plan view showing a film forming apparatus according to an embodiment. [Figure 16] FIG. 16 is a cross-sectional view showing an example of the first processing unit in FIG. 15. MODE FOR CARRYING OUT THE INVENTION
[0008] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In each drawing, the same or corresponding components are denoted by the same reference numerals, and the description thereof may be omitted.
[0009] A film forming method according to an embodiment will be described with reference to FIGS. 1 to 7. The film forming method has, for example, steps S101 to S110 shown in FIG. 1. The film forming method may have at least steps S101, S104 to S109. For example, the film forming method may not have steps S102 to S103. Further, the film forming method may have steps other than steps S101 to S110 shown in FIG. 1.
[0010] Step S101 in FIG. 1 includes preparing a substrate 1 as shown in FIG. 2(A). The substrate 1 has a base substrate 10. The base substrate 10 is, for example, a silicon wafer, a compound semiconductor wafer, or a glass substrate. The substrate 1 has an insulating film 11 and a conductive film 12 in different regions of the substrate surface 1a. The substrate surface 1a is, for example, the upper surface of the substrate 1. The insulating film 11 and the conductive film 12 are formed on the base substrate 10. Another functional film may be formed between the base substrate 10 and the insulating film 11 or between the base substrate 10 and the conductive film 12. The insulating film 11 is an example of the first film, and the conductive film 12 is an example of the second film. The materials of the first film and the second film are not particularly limited. The first film may be a conductive film and the second film may be an insulating film.
[0011] The insulating film 11 is, for example, an interlayer insulating film. The interlayer insulating film is preferably a low dielectric constant (Low-k) film. The insulating film 11 is not particularly limited, but is, for example, a SiO film, a SiN film, a SiC film, a SiOC film, a SiCN film, a SiON film, or a SiOCN film. Here, the SiO film means a film containing silicon (Si) and oxygen (O). The atomic ratio of Si to O in the SiO film is usually 1:2, but the atomic ratio of Si to O in the SiO film in the present application is not limited to 1:2. The same applies to the SiN film, the SiC film, the SiOC film, the SiCN film, the SiON film, and the SiOCN film. The insulating film 11 has recesses on the substrate surface 1a. The recesses are trenches, contact holes or via holes.
[0012] The conductive film 12 is, for example, filled in the recesses of the insulating film 11. The conductive film 12 is, for example, a metal film. The metal film is, for example, a Cu film, a Co film, a Ru film, a W film, or a Mo film. Note that the conductive film 12 may be a cap film. That is, as shown in FIG. 12(A), a second conductive film 15 may be embedded in the recesses of the insulating film 11, and the conductive film 12 may cover the second conductive film 15. The second conductive film 15 is formed of a metal different from the conductive film 12.
[0013] The substrate 1 may further have a third film on the substrate surface 1a. The third film is, for example, a barrier film 13. The barrier film 13 is formed between the insulating film 11 and the conductive film 12 to suppress metal diffusion from the conductive film 12 to the insulating film 11. The barrier film 13 is not particularly limited, but is, for example, a TaN film or a TiN film. Here, the TaN film means a film containing tantalum (Ta) and nitrogen (N). The atomic ratio of Ta to N in the TaN film is not limited to 1:1. The same applies to the TiN film.
[0014] Table 1 summarizes specific examples of the insulating film 11, the conductive film 12, and the barrier film 13.
[0015]
Table 1
[0016] The combination of the insulating film 11, the conductive film 12, and the barrier film 13 is not particularly limited.
[0017] Step S102 in Figure 1 includes cleaning the substrate surface 1a, as shown in Figure 2(B). This removes contaminants 22 (see Figure 2(A)) present on the substrate surface 1a. The contaminants 22 include, for example, at least one of metal oxides and organic matter. The metal oxide is, for example, an oxide formed by the reaction of the conductive film 12 with the atmosphere, and is a so-called native oxide film. The organic matter is, for example, a deposit containing carbon, which adheres to the substrate 1 during the processing process.
[0018] For example, step S102 includes supplying a cleaning gas to the substrate surface 1a. The cleaning gas may be plasma-generated to improve the efficiency of removing contaminants 22. The cleaning gas includes a reducing gas such as H2 gas. The reducing gas removes the contaminants 22. Step S102 is a dry process, but it may also be a wet process.
[0019] An example of the processing conditions for step S102 is shown below. H2 gas flow rate: 200 sccm~3000 sccm Power supply frequency for plasma generation: 400kHz~40MHz Power for plasma generation: 50W~1000W Processing time: 1 second to 60 seconds Processing temperature: 50℃~300℃ Processing pressure: 10 Pa to 7000 Pa.
[0020] Step S103 in Figure 1 includes forming an oxide film 32 by oxidizing the surface of the conductive film 12, as shown in Figure 2(C). For example, step S103 includes forming the oxide film 32 by supplying an oxygen-containing gas to the substrate surface 1a. The oxygen-containing gas includes at least one selected from O2 gas, O3 gas, H2O gas, NO gas, NO2 gas, and N2O gas. Step S103 is a dry process, but it may also be a wet process.
[0021] Since the contaminants 22 have been removed before step S103, step S103 yields an oxide film 32 having the desired film thickness and film quality. Film quality includes the surface state of the film. Unlike native oxide films, the film thickness and film quality of the oxide film 32 can be controlled by the source gas and deposition conditions. By forming an oxide film 32 having the desired film thickness and film quality, a dense self-assembled monolayer (SAM) can be formed on the surface of the conductive film 12 in step S104, which will be described later.
[0022] An example of the processing conditions for step S103 is shown below. O2 gas flow rate: 100 sccm to 2000 sccm Processing time: 10 seconds to 300 seconds Processing temperature: 100℃~250℃ Processing pressure: 200 Pa to 1200 Pa.
[0023] Step S104 in Figure 1, as shown in Figure 2(D), involves selectively forming SAM17 on the surface of the conductive film 12 relative to the surface of the insulating film 11 using a fluorine-free organic compound. SAM17 is formed by supplying a gas of the organic compound into a processing container containing the substrate 1. The organic compound is a precursor of SAM17.
[0024] By using a fluorine-free organic compound as a precursor for SAM17, environmental protection can be contributed to. Compared to fluorine-containing organic compounds, fluorine-free organic compounds leave almost no residue in the processing container containing the substrate 1, thus improving the stability (reproducibility) of the processing quality of the substrate 1.
[0025] The organic compound includes, for example, a first functional group and a second functional group provided at one end of the first functional group. The first functional group is, for example, a hydrocarbon group. The first functional group is preferably a linear chain. The first functional group is preferably an alkyl group. The first functional group may also have an unsaturated bond such as a double bond. The second functional group is chemically adsorbed onto the surface of the conductive film 12.
[0026] The organic compounds used as precursors for SAM17 are not particularly limited, but for example, thiol compounds. Thiol compounds are represented by the general formula "R-SH". R is, for example, a hydrocarbon group and corresponds to the first functional group. The SH group corresponds to the second functional group. A specific example of a thiol compound is CH3(CH2) x CH2SH (where X is an integer between 1 and 16) is one example.
[0027] Thiol compounds are more easily chemisorbed onto the surface of the conductive film 12 than onto the surface of the insulating film 11. Therefore, SAM 17 is selectively formed on the surface of the conductive film 12 compared to the surface of the insulating film 11. SAM 17 is not formed on the surface of the insulating film 11, nor is it formed on the surface of the barrier film 13.
[0028] If the oxide film 32 is formed before the formation of SAM17, the density of SAM17 can be improved compared to when the oxide film 32 is not formed, and the blocking performance of SAM17 can be improved in steps S105 and S109 described later. Since the thiol compound is chemically adsorbed while reducing the oxide film 32, the oxide film 32 does not need to remain after step S104 (see Figures 2(D), 9(D), and 12(D)).
[0029] Furthermore, the precursor of SAM17 is not limited to thiol compounds. For example, the precursor of SAM17 may be an organosilane compound, a phosphonic acid compound, or an isocyanate compound. Organosilane compounds are represented by the general formula "R-Si(OCH3)3" or "R-SiCl3". Phosphonic acid compounds are represented by the general formula "RP(=O)(OH)2". Isocyanate compounds are represented by the general formula "RN=C=O". In these general formulas, R is, for example, a hydrocarbon group.
[0030] An example of the processing conditions for step S104 is shown below. Flow rate of organic compound gas: 50 sccm to 500 sccm Processing time: 10 seconds to 1800 seconds Processing temperature: 100℃~350℃ Processing pressure: 100 Pa to 14000 Pa.
[0031] Step S105 in Figure 1 includes forming a protective film 23 on the surface of the insulating film 11 while inhibiting the formation of the protective film 23 on the surface of the conductive film 12 using SAM 17, as shown in Figure 3(A). The protective film 23 is, for example, an insulating film. The protective film 23 is formed not only on the surface of the insulating film 11 but also on the surface of the barrier film 13.
[0032] The protective film 23 prevents the insulating film 11 from fluorinating by fluorinating it instead of the insulating film 11 in step S106, which will be described later. The protective film 23 only needs to have a thickness sufficient to prevent the insulating film 11 from fluorinating. Its thickness is, for example, 0.1 nm to 2 nm.
[0033] The protective film 23 is not particularly limited, but examples include an AlO film, an SiO film, a SiN film, a ZrO film, or an HfO film. Here, an AlO film means a film containing aluminum (Al) and oxygen (O). The atomic ratio of Al to O in an AlO film is usually 2:3, but the atomic ratio of Al to O in the AlO film in this application is not limited to 2:3. The same applies to SiO films, SiN films, ZrO films, and HfO films.
[0034] The protective film 23 is formed, for example, by the ALD (Atomoic Layer Deposition) method. When forming the protective film 23 by the ALD method, the precursor gas for the protective film 23 and the reaction gas are alternately supplied to the substrate surface 1a. The precursor gas for the protective film 23 contains, for example, a metallic element or a metalloid element.
[0035] The reaction gas reacts with the precursor gas of the protective film 23 to form the protective film 23. The reaction gas is, for example, an oxidizing gas or a nitriding gas. The oxidizing gas forms an oxide film of the metal element or metalloid element contained in the precursor gas. The nitriding gas forms a nitride film of the metal element or metalloid element contained in the precursor gas.
[0036] The method for forming the protective film 23 includes, for example, steps S105a to S105c shown in Figure 5. Note that the order of steps S105a and S105b may be reversed. Furthermore, between steps S105a and S105b, there may be a step in which an inert gas such as argon gas is supplied into the processing container to discharge various gases remaining in the processing container.
[0037] Step S105a includes supplying the precursor gas for the protective film 23 to the substrate surface 1a. Since SAM 17 is formed on the surface of the conductive film 12, the precursor gas is selectively adsorbed onto the surface of the insulating film 11. An example of the processing conditions for step S105a is shown below. In the processing conditions below, TMA (trimethylaluminum) gas is the precursor gas for the AlO film. TMA gas flow rate: 1 sccm to 300 sccm (preferably 50 sccm) Processing time: 0.1 seconds to 2 seconds Processing temperature: 100℃~250℃ Processing pressure: 133 Pa to 1200 Pa.
[0038] Step S105b includes supplying a reaction gas to the substrate surface 1a. The reaction gas reacts with the precursor gas of the protective film 23 to form the protective film 23. An example of the processing conditions for step S105b is shown below. Under the processing conditions below, the H2O gas reacts with the TMA gas to form an AlO film. H2O gas flow rate: 10 sccm to 200 sccm Processing time: 0.1 seconds to 2 seconds Processing temperature: 100℃~250℃ Processing pressure: 133 Pa to 1200 Pa.
[0039] Step S105c includes checking whether steps S105a to S105b have been performed a set number of times (K times). The set number of times (K times) is determined according to the target thickness of the protective film 23, for example, from 1 to 20 times. The target thickness of the protective film 23 is, for example, from 0.1 nm to 2 nm.
[0040] If the number of executions has not reached the set number (K times) (step S105c, NO), the thickness of the protective film 23 has not reached the target thickness, so steps S105a to S105b are performed again. On the other hand, if the number of executions has reached the set number (K times) (step S105c, YES), the thickness of the protective film 23 has reached the target thickness, so the process shown in Figure 5 is completed.
[0041] Step S106 in Figure 1 involves fluorinating SAM17. At least some of the hydrogen atoms in SAM17 are replaced with fluorine atoms. This improves the water repellency and coating properties of SAM17, and enhances the blocking performance of SAM17. The coating properties of SAM17 are improved because fluorine atoms have a larger atomic radius than hydrogen atoms.
[0042] Step S106 also includes fluorinating the protective film 23, as shown in Figure 3(B). In Figure 3(B), the fluorinated portion 23a of the protective film 23 is shown as a dot pattern. The protective film 23 prevents the insulating film 11 from being fluorinated by fluorinating it instead of the insulating film 11. It is sufficient for at least a portion of the protective film 23 to be fluorinated, or the entire protective film 23 may be fluorinated.
[0043] Step S106 includes, for example, supplying a fluorine-containing gas to the substrate surface 1a. The fluorine-containing gas is not particularly limited as long as it contains fluorine, but includes, for example, at least one selected from HF gas, F2 gas, and ClF3 gas.
[0044] An example of the processing conditions for step S106 is shown below. Flow rate of fluorine-containing gas: 50 sccm to 500 sccm Processing time: 1 second to 120 seconds Processing temperature: 100℃~400℃ Processing pressure: 1.333 Pa to 1200 Pa.
[0045] Step S107 in Figure 1 includes etching the fluorinated portion 23a of the protective film 23, as shown in Figure 3(C). This allows the deteriorated portion 23a of the protective film 23 to be removed.
[0046] Step S107 includes, for example, supplying an etching gas to the substrate surface 1a. The etching gas converts the fluorinated portion 23a of the protective film 23 into a volatile compound through a ligand exchange reaction. This etches the fluorinated portion 23a of the protective film 23.
[0047] The etching gas includes at least one selected from, for example, TMA (trimethylaluminum) gas, DMAC (dimethylacetamide) gas, tin(II) acetylacetonate gas, Cl2 gas, BCl3 gas, and TiCl4 gas. These gases convert the fluorinated portion 23a of the protective film 23 into volatile compounds through ligand exchange reactions.
[0048] For example, if the protective film 23 is an AlO film, at least a portion of the AlO film becomes an AlF film through fluorination. When TMA (trimethylaluminum: Al(CH3)3) gas is used as the etching gas, a ligand exchange reaction between the TMA gas and the AlF film produces AlF(CH3)2 gas, which removes the AlF film.
[0049] An example of the processing conditions for step S107 is shown below. Etching gas flow rate: 10 sccm to 500 sccm Processing time: 1 to 30 seconds Processing temperature: 100℃~400℃ Processing pressure: 10 Pa to 1500 Pa.
[0050] Step S108 in Figure 1 includes checking whether step S107 (etching of the fluorinated portion of the protective film) has been performed a set number of times (J times) after step S106 (fluorination of the SAM and protective film) has been performed once, or whether steps S106 and S107 have been performed alternately a set number of times (J times).
[0051] If the number of executions has not reached the set number (J times) (Step S108, NO), the removal of the protective film 23 is insufficient, so either Step S107 is performed again, or Steps S106 and S107 are performed again. On the other hand, if the number of executions has reached the set number (J times) (Step S108, YES), the removal of the protective film 23 is sufficient, so the processes from Step S109 onwards are performed.
[0052] J is an integer greater than or equal to 1, preferably an integer greater than or equal to 2. If J is an integer greater than or equal to 2, step S106 (fluorination of SAM and protective film) is performed once, followed by step S107 (etching of the fluorinated portion of the protective film) being performed multiple times, or steps S106 and S107 are performed alternately multiple times.
[0053] Performing step S106 once and then repeatedly performing step S107 makes it easier to remove the fluorinated portion 23a of the protective film 23. Alternatively, by repeatedly performing steps S106 and S107 alternately, it is possible to remove the entire protective film 23 (though this is not shown in the diagram).
[0054] Step S109 in Figure 1 includes forming the target film 18 on the surface of the protective film 23 while inhibiting the formation of the target film 18 on the surface of the conductive film 12 using the SAM 17, as shown in Figure 3(D). The target film 18 and the protective film 23 may be made of the same material or different materials. As mentioned above, the entire protective film 23 may be removed, in which case the target film 18 will be formed on the surface of the insulating film 11.
[0055] The target film 18 is, for example, an insulating film, which is laminated on the insulating film 11 via a protective film 23, or laminated directly on the insulating film 11. The target film 18 is not particularly limited, but examples include AlO film, SiO film, SiN film, ZrO film, or HfO film. Here, AlO film means a film containing aluminum (Al) and oxygen (O). The atomic ratio of Al to O in an AlO film is usually 2:3, but the atomic ratio of Al to O in the AlO film in this application is not limited to 2:3. The same applies to SiO film, SiN film, ZrO film, and HfO film.
[0056] The target film 18 is formed, for example, by the ALD (Atomoic Layer Deposition) method. When the target film 18 is formed by the ALD method, the precursor gas for the target film 18 and the reaction gas are alternately supplied to the substrate surface 1a. The precursor gas for the target film 18 contains, for example, a metallic element or a metalloid element.
[0057] The reaction gas reacts with the precursor gas of the target film 18 to form the target film 18. The reaction gas is, for example, an oxidizing gas or a nitriding gas. The oxidizing gas forms an oxide film of the metal element or metalloid element contained in the precursor gas. The nitriding gas forms a nitride film of the metal element or metalloid element contained in the precursor gas.
[0058] The method for forming the target film 18 includes, for example, steps S109a to S109c shown in Figure 6. Note that the order of steps S109a and S109b may be reversed. Furthermore, between steps S109a and S109b, there may be a step in which an inert gas such as argon gas is supplied into the processing container to discharge various gases remaining in the processing container.
[0059] Step S109a includes supplying the precursor gas of the target film 18 to the substrate surface 1a. Since SAM 17 is formed on the surface of the conductive film 12, the precursor gas is selectively adsorbed onto the surface of the insulating film 11. An example of the processing conditions for step S109 is shown below. In the processing conditions below, TMA (trimethylaluminum) gas is the precursor gas of the AlO film. TMA gas flow rate: 1 sccm to 300 sccm (preferably 50 sccm) Processing time: 0.1 seconds to 2 seconds Processing temperature: 100℃~250℃ Processing pressure: 133 Pa to 1200 Pa.
[0060] Step S109b includes supplying a reaction gas to the substrate surface 1a. The reaction gas reacts with the precursor gas of the target film 18 to form the target film 18. An example of the processing conditions for step S106 is shown below. Under the processing conditions below, the H2O gas reacts with the TMA gas to form an AlO film. H2O gas flow rate: 10 sccm to 200 sccm Processing time: 0.1 seconds to 2 seconds Processing temperature: 100℃~250℃ Processing pressure: 133 Pa to 1200 Pa.
[0061] Step S109c includes checking whether steps S109a to S109b have been performed a set number of times (L times). The set number of times (L times) is set according to the target film thickness of the target film 18, for example, 20 to 80 times. The target film thickness of the target film 18 is thicker than the target film thickness of the protective film 23. The target film thickness of the target film 18 is, for example, 2 nm to 10 nm.
[0062] If the number of executions has not reached the set number (L times) (step S109c, NO), the film thickness of the target film 18 has not reached the target film thickness, so steps S109a to S109b are performed again. On the other hand, if the number of executions has reached the set number (L times) (step S109c, YES), the film thickness of the target film 18 has reached the target film thickness, so the process in Figure 6 is completed.
[0063] According to this embodiment, the blocking performance of the SAM 17 can be improved by pre-fluorinating the SAM 17 before forming the target film 18. Furthermore, by protecting the insulating film 11 with a protective film 23 when fluorinating the SAM 17, the degradation of the insulating film 11 can be suppressed. The protective film 23 is fluorinated in place of the insulating film 11. The fluorinated portion 23a of the protective film 23 is removed by etching before the formation of the target film 18.
[0064] Incidentally, as shown in Figure 3(D), although SAM17 inhibits the formation of the target film 18, the blocking performance of SAM17 is not perfect, and the target film 18 may extend beyond the surface of the insulating film 11 and form on the surface of the conductive film 12. When the target film 18 is present on the conductive film 12, the wiring resistance of the substrate 1 increases. Therefore, step S110, which will be described later, may be performed.
[0065] Step S110 in Figure 1 includes decomposing the fluorinated SAM 17 and etching the side of the target film 18 adjacent to the SAM 17, as shown in Figure 4(A) or Figure 4(B). The side of the target film 18 can be removed from above the conductive film 12, thereby reducing the wiring resistance of the substrate 1.
[0066] The sides of the target film 18 are removed from above the conductive film 12, leaving the central part of the target film 18 on top of the insulating film 11. As shown in Figure 4(A), the surface of the insulating film 11 does not need to be exposed, or as shown in Figure 4(B), a part of the surface of the insulating film 11 may be exposed. After step S110, it is sufficient that the target film 18 remains on top of the insulating film 11.
[0067] Step S110 includes, for example, steps S110a to S110c shown in Figure 7. The order of steps S110a and S110b may be reversed. Step S110b (supply of plasma gas) may be omitted, and only step S110a (supply of H2O-containing gas) may be performed.
[0068] Step S110a includes supplying an H2O-containing gas to the substrate surface 1a. The H2O-containing gas may consist of H2O gas alone, or it may consist of H2O gas and a carrier gas. In addition to H2O gas, the H2O-containing gas may also contain an organic acid gas such as a carboxylic acid.
[0069] SAM17 is pre-fluorinated and contains fluorine. Therefore, hydrofluoric acid is produced by the reaction of H2O gas with SAM17. The produced hydrofluoric acid reacts with the side of the target film 18, transforming the side of the target film 18 into a volatile compound. As a result, the side of the target film 18 is etched.
[0070] Since hydrofluoric acid is produced by the reaction of H2O gas with SAM17, it is produced only in the vicinity of SAM17. Therefore, the sides of the target film 18 are etched, while the central part of the target film 18 is not etched. Thus, the target film 18 can be left on top of the insulating film 11.
[0071] An example of the processing conditions for step S110a is shown below. H2O gas flow rate: 50 sccm~200 sccm Processing time: 1 second to 30 seconds Processing temperature: 100℃~250℃ Processing pressure: 133 Pa to 1200 Pa.
[0072] Step S110b involves supplying a plasma-forming gas to the substrate surface 1a. The plasma-forming gas is obtained by plasma-forming at least one selected from, for example, H2 gas, Ar gas, N2 gas, and NH3 gas. The plasma-forming gas promotes the decomposition of SAM17 and the generation of hydrofluoric acid. Since hydrofluoric acid is acidic, it is preferable that the plasma-forming gas is a reducing gas or an inert gas plasma-forming gas so that the hydrofluoric acid is not neutralized.
[0073] An example of the processing conditions for step S110b is shown below. H2 gas flow rate: 200 sccm~3000 sccm Ar gas flow rate: 100 sccm to 6000 sccm Percentage of H2 gas in a mixed gas of H2 and Ar gas: 20% to 90% by volume Power supply frequency for plasma generation: 400kHz~40MHz Power for plasma generation: 100W~600W Processing time: 10-30 seconds Processing temperature: 100℃~250℃ Processing pressure: 133 Pa to 1200 Pa.
[0074] Step S110c includes checking whether steps S110a to S110b have been performed the set number of times (M times). If the number of times performed has not reached the set number (M times) (Step S63, NO), the etching of the target film 18 is insufficient, and steps S110a to S220b are performed again. On the other hand, if the number of times performed has reached the set number (M times) (Step S63, YES), the etching of the target film 18 is sufficient, and the process shown in Figure 7 is completed.
[0075] The number of times (M times) set in step S110c may be one, but it is preferable to have multiple times. By dividing the supply of plasma gas into multiple times, the decomposition of SAM17 can be gradually advanced, hydrofluoric acid can be generated over a long period of time, and the target film 18 can be etched over a long period of time. The number of times (M times) set in step S110c is, for example, 5 to 50.
[0076] In Figure 7, the H2O-containing gas and the plasma-forming gas are supplied sequentially, not simultaneously, although they may be supplied simultaneously. In any case, the supply of the plasma-forming gas can decompose SAM17 and promote the generation of hydrofluoric acid. However, supplying the H2O-containing gas and the plasma-forming gas sequentially can prevent the plasma formation of the H2O-containing gas, thus preventing the generation of oxygen radicals and hydroxyl radicals, and preventing oxidation of the substrate surface 1a.
[0077] Step S110 is not limited to that shown in Figure 7. For example, step S110 may include supplying a plasma-treated hydrogen-containing gas to the substrate surface 1a. The hydrogen-containing gas is not particularly limited as long as it contains hydrogen, but may include at least one selected from, for example, H2 gas, H2O gas, NH3 gas, N2H4 gas, and hydrocarbon gases. Hydrocarbon gases include, for example, CH4 gas.
[0078] SAM17 is pre-fluorinated and contains fluorine and carbon. When a plasma-induced hydrogen-containing gas excites SAM17, active species containing fluorine and carbon are generated. The generated active species react with the side of the target film 18, transforming the side of the target film 18 into a volatile compound. As a result, the side of the target film 18 is etched.
[0079] Since the active species containing fluorine and carbon are generated by the reaction between the plasma-induced hydrogen-containing gas and SAM17, they are generated only in the vicinity of SAM17. Therefore, the sides of the target film 18 are etched, while the central part of the target film 18 is not etched. Thus, the target film 18 can be left on the insulating film 11.
[0080] An example of the processing conditions for step S110 when using plasma-treated hydrogen-containing gas is shown below. H2 gas flow rate: 200 sccm~3000 sccm Power supply frequency for plasma generation: 400kHz~40MHz Power for plasma generation: 50W~1000W Processing time: 1 second to 60 seconds Processing temperature: 50℃~300℃ Processing pressure: 10 Pa to 7000 Pa.
[0081] Step S110 may include supplying a plasma-forming gas to the substrate surface 1a to decompose the SAM 17 and fluorine the side of the target film 18 with the active species contained in the decomposed SAM 17, and etching the side of the fluorinated target film 18 with an etching gas. The fluorination of the side of the target film 18 is carried out in the same manner as in step S110b. The etching of the side of the fluorinated target film 18 is carried out in the same manner as in step S107. Fluorination and etching may be repeated.
[0082] If the thickness of the target film 18 remaining after step S110 has reached the second target thickness, the process is terminated. On the other hand, if the thickness of the target film 18 remaining after step S110 has not reached the second target thickness, the process shown in Figure 8 is performed further. The second target thickness may be the same as the target thickness corresponding to the number of times (L times) set in Figure 6, or it may be greater than the target thickness.
[0083] As shown in Figure 1, the SAM 17 is decomposed in the first step S110. Therefore, as shown in Figure 8, steps S103 and S104 are performed again to reform the SAM 17. The subsequent processing differs depending on whether or not a portion of the surface of the insulating film 11 was exposed in the first step S110.
[0084] If, in the first step S110, a portion of the surface of the insulating film 11 is exposed as shown in Figure 4(B) (step S111, YES), then step S105 is performed again to protect the insulating film 11 and the protective film 23 is reformed. After that, steps S106 to S110 are performed again.
[0085] On the other hand, if, as shown in Figure 4(A), the surface of the insulating film 11 is not exposed in the first step S110 and remains covered with the target film 18 (step S111, NO), then protection of the insulating film 11 is unnecessary. In this case, step S105 (formation of protective film) is not performed again, and steps S106 to S110 are performed again.
[0086] Subsequently, if the number of times steps S109 to S110 are performed does not reach the set number (N times) (step S112, NO), the film thickness of the target film 18 has not reached the second target film thickness, so the process from step S103 onwards in Figure 8 is performed again.
[0087] On the other hand, if the number of times steps S109 to S110 is performed reaches the set number (N times) (step S112, YES), the film thickness of the target film 18 has reached the second target film thickness, and the current process is terminated.
[0088] Next, referring to Figures 9 to 11, we will describe the case where the substrate 1 according to the first modified example is processed by the method shown in Figure 1. Note that the substrate 1 shown in Figure 9(A) may be processed by the method shown in Figure 1 and then further processed by the method shown in Figure 8. The differences will be explained below.
[0089] As shown in Figure 9(A), the substrate 1 may have a liner film 14 on its surface 1a in addition to the insulating film 11, conductive film 12, and barrier film 13. The liner film 14 is formed between the conductive film 12 and the barrier film 13. The liner film 14 is formed on top of the barrier film 13 and assists in the formation of the conductive film 12. The conductive film 12 is formed on top of the liner film 14. The liner film 14 is not particularly limited, but for example, it may be a Co film or a Ru film.
[0090] Table 2 shows specific examples of the insulating film 11, conductive film 12, barrier film 13, and liner film 14.
[0091] [Table 2]
[0092] The combination of the insulating film 11, the conductive film 12, the barrier film 13, and the liner film 14 is not particularly limited.
[0093] Step S102 of this modified example includes removing contaminants 22 (see Figure 9(A)), as shown in Figure 9(B). The contaminants 22 are present, for example, on the surface of the conductive film 12 and the surface of the liner film 14. Step S102 exposes the surface of the conductive film 12 and the surface of the liner film 14.
[0094] Step S103 of this modified example includes forming an oxide film 32 by oxidizing the surface of the conductive film 12 and the surface of the liner film 14, as shown in Figure 9(C). This allows for the formation of a dense SAM 17 on the surface of the conductive film 12 and the surface of the liner film 14 in step S104, which will be described later.
[0095] Step S104 of this modified example includes selectively forming SAM17 on the surface of the conductive film 12 and the surface of the liner film 14 on the surface of the insulating film 11, as shown in Figure 9(D). SAM17 is not formed on the surface of the insulating film 11 and is hardly formed on the surface of the barrier film 13.
[0096] Step S105 of this modified example includes forming a protective film 23 on the surface of the insulating film 11 while inhibiting the formation of the protective film 23 on the surface of the conductive film 12 and the surface of the liner film 14 using the SAM 17, as shown in Figure 10(A). Note that the protective film 23 is formed not only on the surface of the insulating film 11 but also on the surface of the barrier film 13.
[0097] Steps S106 to S110 of this modified example (see Figures 10(B) to 10(D) and Figures 11(A) to 11(B)) are carried out in the same manner as steps S106 to S110 of the above embodiment (see Figures 3(B) to 10(D) and Figures 4(A) to 4(B)).
[0098] In this modified example, as in the above embodiment, the blocking performance of the SAM 17 can be improved by pre-fluorinating the SAM 17 before forming the target film 18. Furthermore, by protecting the insulating film 11 with the protective film 23 when fluorinating the SAM 17, the degradation of the insulating film 11 can be suppressed. The protective film 23 is fluorinated in place of the insulating film 11. The fluorinated portion 23a of the protective film 23 is removed by etching before the formation of the target film 18.
[0099] Next, referring to Figures 12 to 14, we will describe the case where the substrate 1 according to the second modified example is processed using the method shown in Figure 1. Note that the substrate 1 shown in Figure 12(A) may be processed using the method in Figure 1 and then further processed using the method in Figure 8. The differences will be explained below.
[0100] As shown in Figure 12(A), the substrate 1 may have a conductive film 12 that acts as a cap film. That is, as shown in Figure 12(A), a second conductive film 15 may be embedded in the recess of the insulating film 11, and the conductive film 12 may cover the second conductive film 15. The second conductive film 15 is formed of a different metal than the conductive film 12.
[0101] Table 3 summarizes specific examples of the conductive film (cap film) 12, barrier film 13, liner film 14, and second conductive film 15.
[0102] [Table 3]
[0103] The combination of the insulating film 11, the conductive film 12, the barrier film 13, the liner film 14, and the second conductive film 15 is not particularly limited.
[0104] Steps S102 to S110 of this modified example (see Figures 12(B) to 12(D), 13(A) to 13(D), and 14(A) to 14(B)) are carried out in the same manner as steps S102 to S110 of the first modified example described above (see Figures 9(B) to 9(D), 10(A) to 10(D), and 11(A) to 11(B)).
[0105] In the above embodiments, the first modified example, and the second modified example, the insulating film 11 corresponds to the first film and the conductive film 12 corresponds to the second film, but the combination of the first film and the second film is not particularly limited.
[0106] Table 4 shows candidate combinations of the first membrane, the second membrane, and the target membrane 18 when the precursor of SAM17 is a thiol compound.
[0107] [Table 4] The candidates listed in Table 4 can be used in any combination. Preferably, the first film is an insulating film, the second film is a conductive film, and the target film 18 formed on the surface of the first film is an insulating film.
[0108] Table 5 shows candidate combinations of the first membrane, the second membrane, and the target membrane 18 when the precursor of SAM17 is a phosphonic acid compound.
[0109] [Table 5] The candidates listed in Table 5 can be used in any combination. Preferably, the first film is an insulating film, the second film is a conductive film, and the target film 18 formed on the surface of the first film is an insulating film.
[0110] Next, with reference to Figure 15, the film deposition apparatus 100 for carrying out the above film deposition method will be described. As shown in Figure 15, the film deposition apparatus 100 has a first processing unit 200A, a second processing unit 200B, a third processing unit 200C, a fourth processing unit 200D, a fifth processing unit (not shown), and a control unit 500. The first processing unit 200A carries out steps S102 to S103 in Figure 1. The second processing unit 200B carries out step S104 in Figure 1. The third processing unit 200C carries out steps S105 and S109 in Figure 1. The fourth processing unit 200D carries out steps S106 to S107 in Figure 1. The fifth processing unit carries out step S110 in Figure 1. The first processing unit 200A, the second processing unit 200B, the third processing unit 200C, the fourth processing unit 200D, and the fifth processing unit have similar structures. Therefore, it is also possible to perform all of steps S102-S107, S109, and S110 in Figure 1 using only the first processing unit 200A. The transport unit 400 transports the substrate 1 to the first processing unit 200A, the second processing unit 200B, the third processing unit 200C, the fourth processing unit 200D, and the fifth processing unit. The control unit 500 controls the first processing unit 200A, the second processing unit 200B, the third processing unit 200C, the fourth processing unit 200D, the fifth processing unit, and the transport unit 400.
[0111] The transport unit 400 includes a first transport chamber 401 and a first transport mechanism 402. The internal atmosphere of the first transport chamber 401 is an atmospheric atmosphere. The first transport mechanism 402 is provided inside the first transport chamber 401. The first transport mechanism 402 includes an arm 403 for holding the substrate 1 and travels along a rail 404. The rail 404 extends in the direction of the arrangement of the carriers C.
[0112] Furthermore, the transport unit 400 includes a second transport chamber 411 and a second transport mechanism 412. The internal atmosphere of the second transport chamber 411 is a vacuum atmosphere. The second transport mechanism 412 is provided inside the second transport chamber 411. The second transport mechanism 412 includes an arm 413 for holding the substrate 1, and the arm 413 is arranged to be movable in the vertical and horizontal directions and rotatable around a vertical axis. The first processing unit 200A, the second processing unit 200B, the third processing unit 200C, the fourth processing unit 200D, and the fifth processing unit are connected to the second transport chamber 411 via different gate valves G.
[0113] Furthermore, the conveying section 400 has a load lock chamber 421 between the first conveying chamber 401 and the second conveying chamber 411. The internal atmosphere of the load lock chamber 421 is switched between a vacuum atmosphere and an atmospheric atmosphere by a pressure regulating mechanism (not shown). This allows the inside of the second conveying chamber 411 to always be maintained in a vacuum atmosphere. It also prevents gas from flowing from the first conveying chamber 401 into the second conveying chamber 411. Gate valves G are provided between the first conveying chamber 401 and the load lock chamber 421, and between the second conveying chamber 411 and the load lock chamber 421.
[0114] The control unit 500 is, for example, a computer and includes a CPU (Central Processing Unit) 501 and a storage medium 502 such as memory. The storage medium 502 stores programs that control various processes performed in the film deposition apparatus 100. The control unit 500 controls the operation of the film deposition apparatus 100 by causing the CPU 501 to execute the programs stored in the storage medium 502. The control unit 500 controls the first processing unit 200A, the second processing unit 200B, the third processing unit 200C, the fourth processing unit 200D, the fifth processing unit and the transport unit 400 to carry out the above-described film deposition method.
[0115] Next, the operation of the film deposition apparatus 100 will be described. First, the first transport mechanism 402 removes the substrate 1 from the carrier C, transports the removed substrate 1 to the load lock chamber 421, and exits the load lock chamber 421. Next, the internal atmosphere of the load lock chamber 421 is switched from an atmospheric atmosphere to a vacuum atmosphere. After that, the second transport mechanism 412 removes the substrate 1 from the load lock chamber 421 and transports the removed substrate 1 to the first processing unit 200A.
[0116] Next, the first processing unit 200A performs steps S102 to S103 in Figure 1. After that, the second transport mechanism 412 removes the substrate 1 from the first processing unit 200A and transports the removed substrate 1 to the second processing unit 200B. During this time, the surrounding atmosphere of the substrate 1 can be maintained in a vacuum atmosphere.
[0117] Next, the second processing unit 200B performs step S104 in Figure 1. After that, the second transport mechanism 412 removes the substrate 1 from the second processing unit 200B and transports the removed substrate 1 to the third processing unit 200C. During this time, the surrounding atmosphere of the substrate 1 can be maintained in a vacuum atmosphere, and the deterioration of the blocking performance of the SAM 17 can be suppressed.
[0118] Next, the third processing unit 200C performs step S105 in Figure 1. After that, the second transport mechanism 412 removes the substrate 1 from the third processing unit 200C and transports the removed substrate 1 to the fourth processing unit 200D. During this time, the surrounding atmosphere of the substrate 1 can be maintained in a vacuum atmosphere, and the deterioration of the blocking performance of the SAM 17 can be suppressed.
[0119] Next, the fourth processing unit 200D performs steps S106 to S107 in Figure 1 a set number of times. After that, the second transport mechanism 412 removes the substrate 1 from the fourth processing unit 200D and transports the removed substrate 1 to the third processing unit 200C. During this time, the surrounding atmosphere of the substrate 1 can be maintained in a vacuum atmosphere, and the deterioration of the blocking performance of the SAM 17 can be suppressed.
[0120] Next, the third processing unit 200C performs step S109 in Figure 1. After that, the second transport mechanism 412 removes the substrate 1 from the third processing unit 200C and transports the removed substrate 1 to the fifth processing unit. During this time, the surrounding atmosphere of the substrate 1 can be maintained in a vacuum atmosphere.
[0121] Next, the fifth processing unit performs step S110 in Figure 1. After that, the second transport mechanism 412 removes the substrate 1 from the fifth processing unit, transports the removed substrate 1 to the load lock chamber 421, and exits the load lock chamber 421. Subsequently, the internal atmosphere of the load lock chamber 421 is switched from a vacuum atmosphere to an atmospheric atmosphere. After that, the first transport mechanism 402 removes the substrate 1 from the load lock chamber 421 and places the removed substrate 1 into the carrier C. Then, the processing of the substrate 1 is completed.
[0122] Furthermore, the film deposition apparatus 100 can also perform steps S103 to S112 shown in Figure 8.
[0123] Next, the first processing unit 200A will be described with reference to Figure 16. Note that the second processing unit 200B, the third processing unit 200C, the fourth processing unit 200D, and the fifth processing unit are configured in the same way as the first processing unit 200A, so their illustration and description will be omitted.
[0124] The first processing unit 200A includes a substantially cylindrical, airtight processing container 210. An exhaust chamber 211 is provided in the center of the bottom wall of the processing container 210. The exhaust chamber 211 has a shape that protrudes downward, for example, a substantially cylindrical shape. An exhaust pipe 212 is connected to the exhaust chamber 211, for example, on the side of the exhaust chamber 211.
[0125] An exhaust source 272 is connected to the exhaust piping 212 via a pressure controller 271. The pressure controller 271 includes a pressure regulating valve, such as a butterfly valve. The exhaust piping 212 is configured to reduce the pressure inside the processing container 210 by the exhaust source 272. The pressure controller 271 and the exhaust source 272 constitute a gas discharge mechanism 270 that discharges gas from inside the processing container 210.
[0126] A transport port 215 is provided on the side of the processing container 210. The transport port 215 is opened and closed by a gate valve G. The substrate 1 is loaded and unloaded between the processing container 210 and the second transport chamber 411 (see Figure 15) through the transport port 215.
[0127] A stage 220, which is a holding part for holding the substrate 1, is provided inside the processing container 210. The stage 220 holds the substrate 1 horizontally with the substrate surface 1a facing upwards. The stage 220 is formed in a substantially circular shape in plan view and is supported by a support member 221. A substantially circular recess 222 is formed on the surface of the stage 220 for placing a substrate 1, for example, with a diameter of 300 mm. The recess 222 has an inner diameter slightly larger than the diameter of the substrate 1. The depth of the recess 222 is set to be approximately the same as the thickness of the substrate 1, for example. The stage 220 is formed of a ceramic material such as aluminum nitride (AlN). Alternatively, the stage 220 may be formed of a metallic material such as nickel (Ni). Instead of the recess 222, a guide ring for guiding the substrate 1 may be provided on the peripheral edge of the surface of the stage 220.
[0128] A lower electrode 223, for example, grounded, is embedded in the stage 220. A heating mechanism 224 is embedded below the lower electrode 223. The heating mechanism 224 is powered by a power supply unit (not shown) based on a control signal from the control unit 500 (see Figure 15), and heats the substrate 1 placed on the stage 220 to a set temperature. If the entire stage 220 is made of metal, the entire stage 220 functions as the lower electrode, so the lower electrode 223 does not need to be embedded in the stage 220. The stage 220 is provided with a plurality (e.g., three) of lifting pins 231 for holding and raising / lowering the substrate 1 placed on the stage 220. The material of the lifting pins 231 may be, for example, ceramics such as alumina (Al2O3) or quartz. The lower ends of the lifting pins 231 are attached to a support plate 232. The support plate 232 is connected via a lifting shaft 233 to a lifting mechanism 234 located outside the processing container 210.
[0129] The lifting mechanism 234 is installed, for example, at the bottom of the exhaust chamber 211. The bellows 235 is provided between the opening 219 for the lifting shaft 233 formed on the lower surface of the exhaust chamber 211 and the lifting mechanism 234. The shape of the support plate 232 may be such that it can move up and down without interfering with the support member 221 of the stage 220. The lifting pin 231 is configured to move up and down between the upper surface of the stage 220 and the lower surface of the stage 220 by the lifting mechanism 234.
[0130] A gas supply unit 240 is provided on the top wall 217 of the processing vessel 210 via an insulating member 218. The gas supply unit 240 forms the upper electrode and faces the lower electrode 223. A high-frequency power supply 252 is connected to the gas supply unit 240 via a matching unit 251. By supplying high-frequency power of 400 kHz to 40 MHz from the high-frequency power supply 252 to the upper electrode (gas supply unit 240), a high-frequency electric field is generated between the upper electrode (gas supply unit 240) and the lower electrode 223, and a capacitively coupled plasma is generated. The plasma generation unit 250 that generates the plasma includes the matching unit 251 and the high-frequency power supply 252. Note that the plasma generation unit 250 is not limited to generating capacitively coupled plasma, but may generate other plasmas such as inductively coupled plasma.
[0131] The gas supply unit 240 includes a hollow gas supply chamber 241. On the lower surface of the gas supply chamber 241, numerous holes 242 are evenly arranged, for example, to distribute and supply the processing gas into the processing container 210. Above the gas supply chamber 241 in the gas supply unit 240, for example, a heating mechanism 243 is embedded. The heating mechanism 243 is heated to a set temperature by being powered from a power supply unit (not shown) based on a control signal from the control unit 500.
[0132] A gas supply mechanism 260 is connected to the gas supply room 241 via a gas supply passage 261. The gas supply mechanism 260 supplies the gas used in at least one of steps S102 to S107, S109, and S110 of Figure 1 to the gas supply room 241 via the gas supply passage 261. Although not shown, the gas supply mechanism 260 includes individual piping for each type of gas, an on / off valve installed in the middle of the individual piping, and a flow controller installed in the middle of the individual piping. When the on / off valve opens the individual piping, gas is supplied from the supply source to the gas supply passage 261. The amount of gas supplied is controlled by the flow controller. On the other hand, when the on / off valve closes the individual piping, the supply of gas from the supply source to the gas supply passage 261 is stopped.
[0133] While embodiments of the film deposition method and film deposition apparatus relating to this disclosure have been described above, this disclosure is not limited to the above embodiments. Various changes, modifications, substitutions, additions, deletions, and combinations are possible within the scope of the claims. These, too, naturally fall within the technical scope of this disclosure. [Explanation of Symbols]
[0134] 1 circuit board 1a Substrate surface 11. Insulating film (first layer) 12. Conductive film (second film) 17 SAM (Self-assembled monolayer) 18 Target membrane
Claims
1. (A) Prepare a substrate having a first film and a second film formed of a different material from the first film in different regions of its surface, (B) A fluorine-free organic compound is used to selectively form a self-assembled monolayer on the surface of the second film relative to the surface of the first film, (C) After (B) above, the protective film is formed on the surface of the first film while inhibiting the formation of the protective film on the surface of the second film using the self-assembled monolayer, (D) After (C) above, the self-assembled monolayer and the protective film are fluorinated, (E) After (D) above, etching the fluorinated portion of the protective film with an etching gas, (F) After (E), the fluorinated self-assembled monolayer is used to inhibit the formation of the target film on the surface of the second film, while the target film is formed on the surface of the protective film or the surface of the first film. It has, A film formation method wherein the protective film is an AlO film and the etching gas is a TMA gas.
2. The organic compound used in (B) above comprises a hydrocarbon group and a functional group provided at one end of the hydrocarbon group, The method for forming a film according to claim 1, wherein the functional group is chemically adsorbed onto the surface of the second film.
3. The method for forming a film according to claim 1 or 2, wherein the thickness of the protective film formed on the surface of the first film in (C) is 2 nm or less.
4. The method for forming a film according to any one of claims 1 to 3, wherein (D) comprises supplying a fluorine-containing gas to the surface of the substrate.
5. The aforementioned fluorine-containing gas is HF gas, F ２ Gas and ClF ３ The method for forming a film according to claim 4, comprising at least one selected from gases.
6. A film formation method according to any one of claims 1 to 5, wherein (D) is performed once and then (E) is repeated multiple times, or (D) and (E) are repeated alternately multiple times.
7. (G) A film formation method according to any one of claims 1 to 6, comprising: (G) Decomposing the self-assembled monolayer after (F); and etching the side portion of the target film adjacent to the self-assembled monolayer.
8. The above (G) is H ２ The film formation method according to claim 7, comprising supplying an oxygen-containing gas to the surface of the substrate.
9. The method for forming a film according to claim 7, wherein (G) comprises supplying a plasma-formed hydrogen-containing gas to the surface of the substrate.
10. The above (G) is TMA (trimethylaluminum) gas, DMAC (dimethylacetamide) gas, tin(II) acetylacetonate gas, Cl ２ Gas, BCl ３ Gas, and TiCl ４ The method for forming a film according to claim 7, comprising supplying at least one selected from gases to the surface of the substrate.
11. The film formation method according to any one of claims 1 to 10, wherein one of the first film and the second film is an insulating film and the other is a conductive film.
12. Processing container and The processing container includes a holding section for holding the substrate inside, A gas supply mechanism that supplies gas to the inside of the processing container, A gas discharge mechanism for discharging gas from inside the processing container, A transport mechanism for loading and unloading the substrate into and from the processing container, A control unit that controls the gas supply mechanism, the gas discharge mechanism, and the transport mechanism, and carries out the film formation method according to any one of claims 1 to 11, A film deposition apparatus equipped with the following features.