Film deposition method and film deposition apparatus

Abstract

To provide a technique using an organic compound without including fluoride as the precursor of a self-assembled monolayer (SAM) and capable of selectively removing a portion of an object film deposited on the SAM.SOLUTION: A film deposition method includes the following (A)-(E): (A) preparing a substrate including first and second films in areas having different surfaces; (B) selectively forming a self-assembled monomolecular film on the surface of the second film using an organic compound without including fluoride; (C) forming the object film on the surface of the first film while hindering the formation of the object film on the surface of the second film using the self-assembled monomolecular film; (D) after (C), forming a part of the object film into fluoridation faster than the remainder of the object film using fluorine containing gas; and (E) after (D), etching the part of the object film faster than the remainder of the object film using etching gas. The part of the object film part is deposited on the self-assembled monomolecular film.SELECTED DRAWING: Figure 1

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 the SAM. After the formation of the target film, at least one of ions and active species is irradiated to excite the SAM and generate active species having fluorine and carbon. Then, the active species having fluorine and carbon reacts with the side portion of the target film adjacent to the 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 of using an organic compound not containing fluorine as a precursor of the SAM and selectively removing a portion of the target film deposited on the SAM.

Means for Solving the Problems

[0005] A film deposition method according to one aspect of the present disclosure includes the following steps (A) to (E): (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 relative to the surface of the first film using a fluorine-free organic compound. (C) After (B), the target film is formed on the surface of the first film while inhibiting the formation of the target film on the surface of the second film using the self-assembled monolayer. (D) After (C), a portion of the target film is fluorinated faster than the rest of the target film using a fluorine-containing gas. (E) After (D), the portion of the target film is etched faster than the rest of the target film using an etching gas. The portion of the target film is deposited on the self-assembled monolayer. The fluorine-containing gas used in (D) above is HF gas, F 2 Gas and ClF 3 Includes at least one selected from gases. [Effects of the Invention]

[0006] According to one aspect of this disclosure, a fluorine-free organic compound can be used as a precursor for the SAM, and the portion deposited on the SAM of the target film can be selectively removed. [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, Figure 2(D) shows the first example of step S104, Figure 2(E) shows the first example of step S105, and Figure 2(F) shows the first example of the result of repeating steps S106 and S107. [Figure 3] Figure 3(A) shows a first example of step S106, and Figure 3(B) shows a first example of step S107. [Figure 4] Figure 4 is a flowchart showing a modified version of Figure 1. [Figure 5] Figure 5(A) shows a second example of step S101, Figure 5(B) shows a second example of step S102, Figure 5(C) shows a second example of step S103, Figure 5(D) shows a second example of step S104, Figure 5(E) shows a second example of step S105, and Figure 5(F) shows a second example of the result of repeating steps S106 and S107. [Figure 6] Figure 6(A) shows a third example of step S101, Figure 6(B) shows a third example of step S102, Figure 6(C) shows a third example of step S103, Figure 6(D) shows a third example of step S104, Figure 6(E) shows a third example of step S105, and Figure 6(F) shows a third example resulting from repeating steps S106 and S107. [Figure 7] Figure 7 is a plan view showing a film deposition apparatus according to one embodiment. [Figure 8] Figure 8 is a cross-sectional view showing an example of the first processing unit shown in Figure 7. [Modes for carrying out the invention]

[0008] Embodiments of this disclosure will be described below with reference to the drawings. In each drawing, the same or corresponding components are denoted by the same reference numerals, and their descriptions may be omitted.

[0009] A film deposition method according to one embodiment will be described with reference to Figures 1 to 3. The film deposition method includes, for example, steps S101 to S109 shown in Figure 1. Note that the film deposition method only needs to include at least steps S101 and S104 to S107. The film deposition method does not need to include, for example, steps S102 to S103. Furthermore, the film deposition method may include steps other than steps S101 to S109 shown in Figure 1.

[0010] Step S101 in Figure 1 includes preparing the substrate 1 as shown in Figure 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 top 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 a first film, and the conductive film 12 is an example of a 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 for example, it is an SiO film, a SiN film, a SiC film, a SiOC film, a SiCN film, a SiON film, or a SiCN film. Here, an SiO film means a film containing silicon (Si) and oxygen (O). The atomic ratio of Si to O in an SiO film is usually 1:2, but the atomic ratio of Si to O in an SiO film in this application is not limited to 1:2. The same applies to SiN films, SiC films, SiOC films, SiCN films, SiON films, and SiCN films. 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 filled, for example, into 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. The conductive film 12 may also be a cap film. That is, as shown in Figure 6(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 different metal than 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 and suppresses the diffusion of metal from the conductive film 12 to the insulating film 11. The barrier film 13 is not particularly limited, and 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] Note that the combination of the insulating film 11, the conductive film 12, and the barrier film 13 is not particularly limited.

[0017] Step S102 in FIG. 1 includes cleaning the substrate surface 1a as shown in FIG. 2(B). Contaminants 22 (see FIG. 2(A)) present on the substrate surface 1a can be removed. The contaminants 22 include, for example, at least one of a metal oxide and an organic substance. The metal oxide is an oxide formed by the reaction of the conductive film 12 with the atmosphere, i.e., a so-called natural oxide film. The organic substance is, for example, a deposit containing carbon and adheres during the processing of the substrate 1.

[0018] For example, step S102 includes supplying a cleaning gas to the substrate surface 1a. The cleaning gas may be made into plasma in order to improve the removal efficiency of the contaminants 22. The cleaning gas includes, for example, a reducing gas such as H2 gas. The reducing gas removes the contaminants 22. Step S102 is a dry process, but may also be a wet process.

[0019] An example of the processing conditions for step S102 is shown below. Flow rate of H2 gas: 200 sccm to 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 includes selectively forming a SAM 17 on the surface of the conductive film 12 on the surface of the insulating film 11 using a fluorine-free organic compound, as shown in Figure 2(D). The SAM 17 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 the SAM 17.

[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 One example is CH2SH (where X is an integer between 1 and 16).

[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 step S105 described later. Since the thiol compound chemically adsorbs while reducing the oxide film 32, the oxide film 32 does not need to remain after step S104 (see Figures 2(D), 5(D), and 6(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 the target film 18 on the surface of the insulating film 11 while inhibiting the formation of the target film 18 on the surface of the conductive film 12 using SAM 17, as shown in Figure 2(E). The target film 18 is, for example, an insulating film. The target film 18 is not particularly limited, but may be, for example, 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.

[0032] 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.

[0033] 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.

[0034] The reaction gas may also be a reducing gas. The reducing gas uses metal elements or metalloid elements contained in the precursor gas to form a metal film or semiconductor film. The target film 18 may be a metal film or a semiconductor film.

[0035] The target film 18 may also be formed by the CVD (Chemical Vapor Deposition) method. When the target film 18 is formed by the CVD method, the precursor gas and reaction gas for the target film 18 are supplied simultaneously to the substrate surface 1a.

[0036] The following describes the process for forming the target film 18 using the ALD method. Step S105 includes steps S105a to S105c, as shown in Figure 1. 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 any remaining gases in the processing container.

[0037] Step S105a 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 S105a 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.

[0038] Step S105b 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 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 film thickness of the target film 18, for example, between 20 and 80 times.

[0040] If the number of executions has not reached the set number (K ​​times) (step S105c, NO), the film thickness of the target film 18 has not reached the target film 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 film thickness of the target film 18 has reached the target film thickness, so the processes from step S106 onwards are performed.

[0041] Incidentally, as shown in Figure 2(E), the SAM 17 inhibits the formation of the target film 18, but the blocking performance of the SAM 17 is not perfect, and the target film 18 protrudes laterally from the surface of the insulating film 11. A portion 18a of the target film 18 is deposited on top of the SAM 17. When a portion 18a of the target film 18 covers the surface of the conductive film 12, the wiring resistance of the substrate 1 increases, so a portion 18a of the target film 18 is removed from the surface of the conductive film 12, as will be described later.

[0042] Step S106 in Figure 1 includes fluorinating a portion 18a of the target film 18 faster than the rest 18b of the target film 18 using a fluorine-containing gas, as shown in Figure 3(A). In Figure 3(A), the fluorinated portion of the target film 18 is shown as a dot pattern. The portion 18a of the target film 18 is not only fluorinated more deeply from the top downwards than the rest 18b of the target film 18, but is also fluorinated from the sides, unlike the rest 18b of the target film 18.

[0043] A portion 18a of the target film 18 is deposited on the SAM 17 and contains organic compounds. Therefore, fluorination proceeds more readily in this portion 18a of the target film 18 than in the remaining portion 18b of the target film 18. 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 a portion 18a of the target film 18 faster than the remainder 18b of the target film 18 using an etching gas, as shown in Figure 3(B). The etching gas is not particularly limited, but includes at least one selected from, for example, H2 gas, NH3 gas, N2 gas, and Ar gas, and may also be a mixture of these gases (for example, a mixture of H2 gas and Ar gas), and is supplied to the substrate surface 1a in a plasma state.

[0046] Plasma-activated H2 gas, NH3 gas, N2 gas, or Ar gas, or a mixture thereof, activates the fluorinated portions of the target film 18, converting them into volatile compounds. This etches the fluorinated portions of the target film 18. The etching rate depends on the degree of fluorination; the more advanced the fluorination, the faster the etching rate.

[0047] Since a portion 18a of the target film 18 is more fluorinated than the remaining portion 18b of the target film 18, it has a faster etching rate. Therefore, a portion 18a of the target film 18 is removed from the conductive film 12, while the remaining portion 18b of the target film 18 remains on the insulating film 11.

[0048] An example of the processing conditions for step S107 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.

[0049] Step S108 includes checking whether the first cycle C1 has been performed a set number of times (L times). The first cycle C1 includes steps S106 to S107. The set number of times (L times) should be set so that a portion 18a of the target film 18 can be removed, and may be just once, but multiple times is preferable. By repeating the first cycle C1 multiple times, the etching amount can be increased. The set number of times (L times) is, for example, 1 to 50.

[0050] If the number of times the first cycle C1 is performed has not reached the set number (L times) (step S108, NO), a portion 18a of the target film 18 has not been removed, so the first cycle C1 is performed again. On the other hand, if the number of times the first cycle C1 is performed has reached the set number (L times) (step S108, YES), a portion 18a of the target film 18 has been removed, so the processing from step S109 onwards is performed.

[0051] Step S109 includes checking whether the second cycle C2 has been performed a set number of times (M times). The second cycle C2 includes steps S104 to S107. In each second cycle C2, after performing steps S104 to S105, the first cycle C1 is repeatedly performed.

[0052] The second cycle C2 may also include step S103. If SAM17 remains on the surface of the conductive film 12 after step S107, the second cycle C2 may also include step S102. The plasma-treated H2 gas used in step S102 decomposes and removes the SAM17.

[0053] The number of times set in step S109 (M times) is set so that the thickness of the target film 18 remaining on the surface of the insulating film 11 becomes the second target thickness. The second target thickness may be the same as the target thickness corresponding to the number of times set in step S105c (K times), or it may be greater than the target thickness. The number of times set in step S109 (M times) is, for example, 1 to 10.

[0054] If the number of times the second cycle C2 is performed has not reached the set number (M times) (step S109, NO), the thickness of the target film 18 remaining on the surface of the insulating film 11 has not reached the second target thickness, so the second cycle C2 is performed again. On the other hand, if the number of times the second cycle C2 is performed has reached the set number (M times) (step S109, YES), the thickness of the target film 18 remaining on the surface of the insulating film 11 has reached the second target thickness, so the current process is terminated.

[0055] Next, a modified version of Figure 1 will be described with reference to Figure 4. The differences will be described below. In this modified version, step S107 includes at least one etching gas selected from TMA (trimethylaluminum) gas, DMAC (dimethylacetamide) gas, tin(II) acetylacetonate gas, Cl2 gas, BCl3 gas, and TiCl4 gas.

[0056] TMA gas, DMAC gas, tin(II) acetylacetonate gas, Cl2 gas, BCl3 gas, or TiCl4 gas convert the fluorinated portions of the target film 18 into volatile compounds via a ligand exchange reaction. This etches the fluorinated portions of the target film 18. The etching rate depends on the degree of fluorination, with faster etching rates occurring as fluorination progresses.

[0057] Since a portion 18a of the target film 18 is more fluorinated than the remaining portion 18b of the target film 18, it has a faster etching rate. Therefore, a portion 18a of the target film 18 is removed from the conductive film 12, while the remaining portion 18b of the target film 18 remains on the insulating film 11.

[0058] 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.

[0059] Unlike plasma-treated H2 gas, the TMA gas, DMAC gas, tin(II) acetylacetonate gas, Cl2 gas, BCl3 gas, or TiCl4 gas used in step S107 do not decompose SAM17. Therefore, the second cycle C2 includes step S102. The plasma-treated H2 gas used in step S102 decomposes and removes SAM17.

[0060] Next, referring to Figure 5, we will describe the case where the substrate 1 according to the first modified example is processed using the method shown in Figure 1. Note that the substrate 1 shown in Figure 5(A) may also be processed using the method shown in Figure 4. The differences will be explained below.

[0061] As shown in Figure 5(A), the substrate 1 has an insulating film 11, a conductive film 12, a barrier film 13, and a liner film 14 on its substrate surface 1a. 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.

[0062] Table 2 shows specific examples of the insulating film 11, conductive film 12, barrier film 13, and liner film 14.

[0063] [Table 2]

[0064] The combination of the insulating film 11, the conductive film 12, the barrier film 13, and the liner film 14 is not particularly limited.

[0065] Step S102 of this modified example includes removing contaminants 22 (see Figure 5(A)), as shown in Figure 5(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.

[0066] 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 5(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.

[0067] 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 5(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.

[0068] Step S105 of this modified example includes forming the target film 18 on the surface of the insulating film 11 while inhibiting the formation of the target film 18 on the surface of the conductive film 12 and the surface of the liner film 14 using the SAM 17, as shown in Figure 5(E).

[0069] As shown in Figure 5(E), the SAM 17 inhibits the formation of the target film 18, but the blocking performance of the SAM 17 is not perfect, and the target film 18 protrudes laterally from the surface of the insulating film 11. A portion 18a of the target film 18 is deposited on top of the SAM 17.

[0070] In this modified example, as in the above embodiment, by performing steps S106 to S107, a portion 18a of the target film 18 can be removed, as shown in Figure 5(F). While a portion 18a of the target film 18 is removed from the conductive film 12, the remaining portion 18b of the target film 18 remains on the insulating film 11.

[0071] Next, referring to Figure 6, 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 6(A) may also be processed using the method shown in Figure 4. The differences will be explained below.

[0072] As shown in Figure 6(A), the substrate 1 may have a conductive film 12 that acts as a cap film. In other words, as shown in Figure 6(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.

[0073] Table 3 summarizes specific examples of the conductive film (cap film) 12, barrier film 13, liner film 14, and second conductive film 15.

[0074] [Table 3]

[0075] 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.

[0076] Steps S102 to S107 of this modified example (see Figures 6(B) to 6(F)) are carried out in the same manner as steps S102 to S107 of the first modified example (see Figures 5(B) to 5(F)).

[0077] 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. The first film may be a conductive film and the second film may be an insulating film.

[0078] 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.

[0079] [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.

[0080] 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.

[0081] [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.

[0082] Next, with reference to Figure 7, the film deposition apparatus 100 for carrying out the above film deposition method will be described. As shown in Figure 7, 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 transport unit 400, 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 step S105 in Figure 1. The fourth processing unit 200D carries out steps S106 to S107 in Figure 1. The first processing unit 200A, the second processing unit 200B, the third processing unit 200C, and the fourth processing unit 200D have similar structures. Therefore, it is also possible to carry out all of steps S102 to S107 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, and the fourth processing unit 200D. 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, and the transport unit 400.

[0083] 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.

[0084] 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, and the fourth processing unit 200D are connected to the second transport chamber 411 via different gate valves G.

[0085] 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.

[0086] 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, and the transport unit 400 to carry out the above-described film deposition method.

[0087] 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.

[0088] Next, the first processing unit 200A performs steps S102 to S103. 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, and oxidation of the substrate 1 can be suppressed.

[0089] Next, the second processing unit 200B performs step S104. 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.

[0090] Next, the third processing unit 200C performs step S105. Steps S105a to S105b are repeated in the same processing container. 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.

[0091] Next, the fourth processing unit 200D performs steps S106 to S107. Subsequently, the control unit 500 checks whether the first cycle C1 has been performed the set number of times (L times) (step S108). If the number of times the first cycle C1 has been performed has not reached the set number (L times), the fourth processing unit 200D performs the first cycle C1 again. Steps S106 to S107 are repeated in the same processing container.

[0092] Next, the control unit 500 checks whether the second cycle C2 has been performed the set number of times (M times). If the number of times the second cycle C2 has been performed has not reached the set number (M times) (step S109, NO), the second transport mechanism 412 removes the substrate 1 from the fourth processing unit 200D and transports the removed substrate 1 to the first processing unit 200A. After that, the control unit 500 performs the second cycle C2 again.

[0093] On the other hand, if the number of times the second cycle C2 is performed reaches the set number (M times), the second transport mechanism 412 removes the substrate 1 from the fourth processing unit 200D, 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.

[0094] Next, the first processing unit 200A will be described with reference to Figure 8. Note that the second processing unit 200B, the third processing unit 200C, and the fourth processing unit 200D are configured similarly to the first processing unit 200A, and therefore their illustrations and descriptions are omitted.

[0095] 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.

[0096] 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.

[0097] 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 7) through the transport port 215.

[0098] 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.

[0099] 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 7), 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 and 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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 in 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.

[0104] 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]

[0105] 1 circuit board 1a Substrate surface 11. Insulating film (first layer) 12. Conductive film (second film) 17 SAM (Self-assembled monolayer) 18 Target membrane 18a part 18b remainder

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 self-assembled monolayer is used to inhibit the formation of the target film on the surface of the second film while forming the target film on the surface of the first film, (D) After (C) above, a portion of the target film is fluorinated using a fluorine-containing gas at a faster rate than the rest of the target film, (E) After (D) above, etching a portion of the target film faster than the rest of the target film using an etching gas, It has, The aforementioned portion of the target film is deposited on the self-assembled monolayer, A film formation method wherein the fluorine-containing gas used in (D) above includes at least one selected from HF gas, F2 gas, and ClF3 gas.

2. (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 self-assembled monolayer is used to inhibit the formation of the target film on the surface of the second film while forming the target film on the surface of the first film, (D) After (C) above, a portion of the target film is fluorinated using a fluorine-containing gas at a faster rate than the rest of the target film, (E) After (D) above, etching a portion of the target film faster than the rest of the target film using an etching gas, It has, The aforementioned portion of the target film is deposited on the self-assembled monolayer, A film deposition method wherein the etching gas used in (E) above comprises at least one selected from H2 gas, NH3 gas, N2 gas, and Ar gas, and is supplied to the surface of the substrate in a plasma state.

3. (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 self-assembled monolayer is used to inhibit the formation of the target film on the surface of the second film while forming the target film on the surface of the first film, (D) After (C) above, a portion of the target film is fluorinated using a fluorine-containing gas at a faster rate than the rest of the target film, (E) After (D) above, etching a portion of the target film faster than the rest of the target film using an etching gas, It has, The aforementioned portion of the target film is deposited on the self-assembled monolayer, A film deposition method comprising repeating the first cycle, which includes (D) and (E), multiple times.

4. (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 self-assembled monolayer is used to inhibit the formation of the target film on the surface of the second film while forming the target film on the surface of the first film, (D) After (C) above, a portion of the target film is fluorinated using a fluorine-containing gas at a faster rate than the rest of the target film, (E) After (D) above, etching a portion of the target film faster than the rest of the target film using an etching gas, It has, The aforementioned portion of the target film is deposited on the self-assembled monolayer, A film formation method comprising repeating a second cycle including (B), (C), (D), and (E) multiple times.

5. The film formation method according to claim 4, wherein in each of the second cycles, after performing (B) and (C), the first cycle including (D) and (E) is repeated multiple times.

6. 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 any one of claims 1 to 5, wherein the functional group is chemically adsorbed onto the surface of the second film.

7. The fluorine-containing gas used in (D) above is HF gas, F ２ Gas and ClF ３ A method for forming a film according to any one of claims 2 to 5, comprising at least one selected from gases.

8. The etching gas used in (E) above is H ２ Gas, NH ３ Gas, N ２ A film deposition method according to any one of claims 1 and 3 to 5, comprising at least one selected from gas and Ar gas, supplied to the surface of the substrate in a plasma state.

9. The etching gas used in (E) above is TMA (trimethylaluminum) gas, DMAC (dimethylacetamide) gas, tin(II) acetylacetonate gas, Cl ２ Gas, BCl ３ Gas, and TiCl ４ A method for forming a film according to any one of claims 1 and 3 to 5, comprising at least one selected from gases.

10. The film formation method according to claim 1 or 2, wherein the first cycle including (D) and (E) is repeated multiple times.

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. The method for forming a film according to claim 11, wherein the conductive film is a Cu film, a Co film, a Ru film, a W film, or a Mo film.

13. 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 12, A film deposition apparatus equipped with the following features.

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