WO2022070909A1 - Film deposition method and film deposition device - Google Patents

Film deposition method and film deposition device Download PDF

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Publication number
WO2022070909A1
WO2022070909A1 PCT/JP2021/033864 JP2021033864W WO2022070909A1 WO 2022070909 A1 WO2022070909 A1 WO 2022070909A1 JP 2021033864 W JP2021033864 W JP 2021033864W WO 2022070909 A1 WO2022070909 A1 WO 2022070909A1
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Prior art keywords
film
gas
substrate
region
target
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PCT/JP2021/033864
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French (fr)
Japanese (ja)
Inventor
有美子 河野
進一 池
秀司 東雲
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東京エレクトロン株式会社
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Publication of WO2022070909A1 publication Critical patent/WO2022070909A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers

Definitions

  • This disclosure relates to a film forming method and a film forming apparatus.
  • Patent Documents 1 and 2 a self-assembled monolayer (SELf-Assembled Monolayer: SAM) is used to form a target film on the rest of the substrate surface while inhibiting the formation of the target film on a part of the substrate surface.
  • SAM self-assembled monolayer
  • Non-Patent Document 1 describes atomic layer etching (ALE) in which hydrofluoric acid and TMA (trimethylaluminum) are alternately supplied to the surface of an aluminum oxide film to etch the surface of the aluminum oxide film. Have been described.
  • ALE atomic layer etching
  • One aspect of the present disclosure provides a technique for inhibiting the formation of a target membrane using SAM and then selectively removing an unnecessary portion of the target membrane.
  • the film forming method of one aspect of the present disclosure includes the following (A) to (D).
  • a substrate having a first region on which the first film is exposed and a second region on which the second film formed of a material different from the first film is exposed is prepared.
  • An organic compound containing fluorine, which is a raw material for a self-assembled monolayer, is supplied to the surface of the substrate, and the second region is selectively selected among the first region and the second region. To form the self-assembled monolayer.
  • C Using the self-assembled monolayer, the target membrane is formed in the first region while inhibiting the formation of the target membrane in the second region.
  • a gas containing H2O is supplied to the surface of the substrate, and the end portion of the target film protruding from the first region is etched.
  • unnecessary parts of the target membrane can be selectively removed.
  • FIG. 1 is a flowchart showing a film forming method according to an embodiment.
  • FIG. 2A is a diagram showing step S1 of the substrate according to the embodiment.
  • FIG. 2B is a diagram showing step S5 of the substrate according to the embodiment.
  • FIG. 2C is a diagram showing step S6 of the substrate according to the embodiment.
  • FIG. 2D is a diagram showing an example of step S7 of the substrate according to the embodiment.
  • FIG. 3 is a flowchart showing an example of the subroutine in step S6.
  • FIG. 4 is a flowchart showing an example of the subroutine in step S7.
  • FIG. 5A is a diagram showing step S1 of the substrate according to the first modification.
  • FIG. 5B is a diagram showing step S5 of the substrate according to the first modification.
  • FIG. 5A is a diagram showing step S1 of the substrate according to the first modification.
  • FIG. 5B is a diagram showing step S5 of the substrate according to the first modification.
  • FIG. 5C is a diagram showing step S6 of the substrate according to the first modification.
  • FIG. 5D is a diagram showing an example of step S7 of the substrate according to the first modification.
  • FIG. 6A is a diagram showing step S1 of the substrate according to the second modification.
  • FIG. 6B is a diagram showing step S5 of the substrate according to the second modification.
  • FIG. 6C is a diagram showing step S6 of the substrate according to the second modification.
  • FIG. 6D is a diagram showing an example of step S7 of the substrate according to the second modification.
  • FIG. 7 is a plan view showing a film forming apparatus according to an embodiment.
  • FIG. 8 is a cross-sectional view showing an example of the first processing unit of FIG. 7.
  • FIG. 9 is an SEM photograph of a cross section of the substrate obtained in Example 5.
  • the film forming method includes, for example, steps S1 to S8 shown in FIG.
  • the film forming method may include at least steps S1 and S5 to S8, and may not include, for example, steps S2 to S4. Further, the film forming method may include steps other than steps S1 to S8 shown in FIG.
  • the substrate 1 is prepared as shown in FIG. 2A.
  • Preparing the substrate 1 includes, for example, carrying the carrier C into the film forming apparatus 100 shown in FIG. 7.
  • the carrier C accommodates a plurality of substrates 1.
  • the substrate 1 has a base substrate 10 such as a silicon wafer or a compound semiconductor wafer.
  • the compound semiconductor wafer is not particularly limited, and is, for example, a GaAs wafer, a SiC wafer, a GaN wafer, or an InP wafer.
  • the substrate 1 has an insulating film 11 formed on the base substrate 10.
  • a conductive film or the like may be formed between the insulating film 11 and the base substrate 10.
  • 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 SiOC film, a SiON film, or a SiOCN film.
  • the SiO film means a film containing silicon (Si) and oxygen (O).
  • the atomic ratio of Si to O in the SiO film is not limited to 1: 1. The same applies to the SiN film, the SiOC film, the SiON film, and the SiOCN film.
  • the insulating film 11 has a recess on the surface 1a of the substrate 1.
  • the recess is a trench, contact hole or via hole.
  • the substrate 1 has a metal film 12 that is filled inside the recess.
  • the metal film 12 is not particularly limited, but is, for example, a Cu film, a Co film, a Ru film, or a W film.
  • the substrate 1 further has a barrier membrane 13 formed along the recesses.
  • the barrier film 13 suppresses metal diffusion from the metal 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.
  • 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.
  • Table 1 summarizes specific examples of the insulating film 11, the metal film 12, and the barrier film 13.
  • the combination of the insulating film 11, the metal film 12, and the barrier film 13 is not particularly limited.
  • the substrate 1 has a first region A1 in which the insulating film 11 is exposed and a second region A2 in which the metal film 12 is exposed on the surface 1a thereof. Further, the substrate 1 may further have a third region A3 on the surface 1a on which the barrier membrane 13 is exposed. The third region A3 is formed between the first region A1 and the second region A2.
  • the structure of the substrate 1 is not limited to the structure shown in FIG. 2A, as will be described later.
  • step S2 of FIG. 1 the surface 1a of the substrate 1 is cleaned.
  • a reducing gas such as H 2 gas is supplied to the surface 1a of the substrate 1 to remove the natural oxide film formed on the surface 1a of the substrate 1.
  • the natural oxide film is formed on the surface of the metal film 12, for example.
  • the reducing gas may be plasmatized. Further, the reducing gas may be used by mixing with a rare gas such as Ar gas.
  • step S2 An example of the processing conditions in step S2 is shown below.
  • H2 gas flow rate 500 sccm - 2000 sccm
  • Ar gas flow rate 300 sccm-6000 sccm
  • Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas 30% by volume to 90% by volume
  • Power frequency for plasma generation 40MHz
  • Power for plasma generation 200W
  • Processing time 10 sec to 30 sec
  • Processing temperature (board temperature) 120 ° C
  • Processing pressure 266 Pa.
  • step S3 of FIG. 1 the surface 1a of the substrate 1 is oxidized.
  • a gas containing oxygen such as O 2 gas is supplied to the surface 1a of the substrate 1 to appropriately oxidize the surface of the metal film 12. Since the natural oxide film has been removed in advance, the density of oxygen atoms becomes the desired density.
  • step S5 described later a dense self-assembled monolayer (SAM) can be formed on the surface of the metal film 12.
  • step S3 An example of the processing conditions in step S3 is shown below.
  • O 2 gas flow rate 100 sccm-2000 sccm Processing time: 300 sec to 900 sec (preferably 600 sec) Processing temperature: 120 ° C Processing pressure: 200 Pa to 1200 Pa.
  • step S4 of FIG. 1 IPA (isopropanol Alcohol) gas is supplied to the surface 1a of the substrate 1.
  • IPA gas flow rate 10 sccm-200 sccm
  • Processing time 0 sec to 900 sec
  • Processing temperature 150 ° C
  • Processing pressure 300Pa-400Pa
  • the processing time may be 0 sec, that is, step S4 may be omitted.
  • an organic compound containing fluorine which is a raw material of SAM 17 is supplied to the surface 1a of the substrate 1, and as shown in FIG. 2B, in the first region A1 and the second region A2. Then, SAM17 is selectively formed in the second region A2.
  • the raw material of SAM17 is not particularly limited, but is, for example, a thiol-based compound.
  • the thiol-based compound has hydrogenated sulfur in the head group and is represented by the general formula "R-SH".
  • R is, for example, a hydrocarbon group in which at least a part of hydrogen is replaced with fluorine.
  • Specific examples of thiol compounds include CF 3 (CF 2 ) 5 CH 2 CH 2 SH (1H, 1H, 2H, 2H-perfluorooctane thiol: PFOT), and CF 3 (CF 2 ) 7 CH 2 CH 2 SH. (1H, 1H, 2H, 2H-perfluorodecanethiol: PFDT) can be mentioned.
  • Thiol compounds are more easily chemisorbed on the conductive film than the insulating film.
  • the SAM 17 is selectively formed in the second region A2 in the first region A1 and the second region A2. Will be done.
  • Examples of the conductive film that chemically adsorbs a thiol compound include a nitride film such as a TaN film in addition to a metal film. Therefore, the SAM 17 is formed not only in the second region A2 but also in the third region A3. However, the thiol compound is more easily chemically adsorbed to the metal film than the nitride film. Therefore, the SAM 17 is more likely to be formed in the second region A2 than in the third region A3.
  • the raw material of SAM17 is not limited to thiol compounds.
  • the raw material of SAM17 may be a phosphonic acid-based compound.
  • R is, for example, a hydrocarbon group in which at least a part of hydrogen is replaced with fluorine.
  • step S5 An example of the processing conditions in step S5 is shown below.
  • PFOT gas flow rate 80 sccm-200 sccm
  • Processing time 90 sec to 900 sec (preferably 300 sec)
  • Processing temperature 150 ° C
  • Processing pressure 200Pa-4000Pa.
  • the target film 18 is formed in the first region A1 while inhibiting the formation of the target film 18 in the second region A2 using SAM17.
  • the target film 18 is, for example, an insulating film, and is formed on the insulating film 11.
  • the SAM 17 is formed not only in the second region A2 but also in the third region A3.
  • the target film 18 is formed in the first region A1 while inhibiting the formation of the target film 18 in the second region A2 and the third region A3 using the SAM 17.
  • the target film 18 is not particularly limited, but is, for example, an AlO film, a SiO film, a SiN film, a ZrO film, an HfO film, or the like.
  • the AlO film means a film containing aluminum (Al) and oxygen (O).
  • the atomic ratio of Al to O in the AlO film is not limited to 1: 1.
  • the target film 18 is formed by a CVD (Chemical Vapor Deposition) method or an ALD (Atomic Layer Deposition) method.
  • an Al-containing gas such as TMA (trimethylaluminum) gas and an oxidizing gas such as water vapor ( H2O gas) are alternately supplied to the surface 1a of the substrate 1. ..
  • the method for forming an AlO film includes, for example, steps S61 to S65 shown in FIG.
  • step S61 the Al-containing gas is supplied to the surface 1a of the substrate 1.
  • step S62 an inert gas such as Ar gas is supplied to the surface 1a of the substrate 1 to purge the excess Al-containing gas that has not been chemically adsorbed on the surface 1a of the substrate 1.
  • step S63 the oxidation gas is supplied to the surface 1a of the substrate 1.
  • step S64 an inert gas such as Ar gas is supplied to the surface 1a of the substrate 1 to purge the excess oxidizing gas that has not been chemically adsorbed on the surface 1a of the substrate 1.
  • the order of steps S61 and S63 may be reversed.
  • step S65 it is checked whether or not steps S61 to S64 have been executed a set number of times. If the number of executions has not reached the set number of times (steps S65, NO), steps S61 to S64 are executed again. On the other hand, when the number of times of implementation has reached the set number of times (step S65, YES), the film thickness of the AlO film has reached the target film thickness, so the current process is terminated.
  • the number of times of setting in step S65 is set according to the target film thickness of the AlO film, and is, for example, 20 to 80 times.
  • step S6 An example of the processing conditions in step S6 is shown below.
  • TMA gas flow rate 50 sccm Processing time: 0.1 sec to 2 sec -Step S62 Ar gas flow rate: 1000 sccm-8000 sccm Processing time: 0.5 sec to 2 sec -Step S63 H2 O gas flow rate: 50 sccm- 200 sccm Processing time: 0.5 sec to 2 sec -Step S64 Ar gas flow rate: 1000 sccm-8000 sccm Processing time: 0.5 sec to 5 sec -Processing conditions common to steps S61 to S64 Processing temperature: 100 ° C to 250 ° C Processing pressure: 133 Pa to 1200 Pa.
  • 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 first region A1.
  • the width W of the protruding portion, that is, the unnecessary portion is, for example, about 2 nm to 10 nm.
  • step S7 a gas containing H2O is supplied to the surface 1a of the substrate 1.
  • Hydrofluoric acid is produced by the reaction between the gas containing H2O and SAM17.
  • the target film 18 can be etched with the generated hydrofluoric acid.
  • the product produced by etching is volatile, vaporized and exhausted.
  • the target film 18 is, for example, an AlO film, a SiO film, a SiN film, a ZrO film, an HfO film, or the like. All of these films can be etched with hydrofluoric acid.
  • hydrofluoric acid is produced by the reaction of a gas containing H2O with SAM17. Therefore, hydrofluoric acid is generated only in the vicinity of SAM17. Therefore, the unnecessary portion protruding from the first region A1 of the target film 18 is etched, whereas the necessary portion formed in the first region A1 of the target film 18 is not etched. Therefore, unnecessary portions of the target film 18 can be selectively removed.
  • Non-Patent Document 1 describes atomic layer etching (ALE) in which hydrofluoric acid and TMA are alternately supplied to the surface of an ALO film to etch the surface of the ALO film.
  • ALE atomic layer etching
  • the processing temperature is high (for example, 300 ° C. or higher, preferably 350 ° C. or higher), and the substrate 1 may be damaged. Specific examples of damage include fluorination or alloying of the metal film 12. The alloying occurs by the reaction between the metal contained in the raw material gas (for example, TMA) of the target film 18 and the metal film 12.
  • the unnecessary portion protruding from the first region A1 of the target film 18 is etched, whereas the necessary portion formed in the first region A1 of the target film 18 is Not etched. Therefore, unnecessary portions of the target film 18 can be selectively removed. As a result, the wiring resistance of the substrate 1 can be reduced. Further, in step S7 of the present embodiment, the processing temperature is, for example, 200 ° C. or lower. Therefore, it is possible to suppress the occurrence of damage to the substrate 1.
  • Step S7 in FIG. 1 includes, for example, steps S71 to S73 shown in FIG.
  • a gas containing H 2 O (a gas containing H 2 O) is supplied to the surface 1a of the substrate 1.
  • the H 2 O-containing gas may contain only the H 2 O gas, or may contain the H 2 O gas and the carrier gas. Further, the H 2 O-containing gas may contain an organic acid gas such as a carboxylic acid in addition to the H 2 O gas.
  • a plasmatized gas (plasmaized gas) is supplied to the surface 1a of the substrate 1.
  • the plasmatized gas comprises at least one selected from, for example, H 2 gas, Ar gas, N 2 gas, and NH 3 gas.
  • the supply of plasmatized gas can decompose SAM17 and promote the production of hydrofluoric acid. Since hydrofluoric acid is acidic, the plasmatized gas is preferably a reducing gas or an inert gas so that the hydrofluoric acid is not neutralized.
  • the order of steps S71 and S72 may be reversed.
  • step S73 it is checked whether or not steps S71 to S72 have been executed a set number of times. If the number of executions has not reached the set number of times (steps S73, NO), steps S71 to S72 are executed again. On the other hand, when the number of executions has reached the set number of times (step S73, YES), the current process is terminated.
  • the H2O -containing gas and the plasmatized gas are supplied in order and are not supplied at the same time, but may be supplied at the same time.
  • the supply of plasmatized gas can decompose SAM17 and promote the production of hydrofluoric acid.
  • the H 2 O-containing gas and the plasmatized gas are supplied in order, the H 2 O-containing gas can be prevented from being plasmatized, the generation of oxygen plasma can be prevented, and the oxidation of the surface 1a of the substrate 1 can be prevented.
  • the number of times of setting in step S73 may be once, but is preferably a plurality of times.
  • the decomposition of SAM 17 can be gradually promoted, hydrofluoric acid can be generated over a long period of time, and the width W of an unnecessary portion can be narrowed.
  • the number of times of setting in step S73 is, for example, 5 to 50.
  • step S7 An example of the processing conditions in step S7 is shown below.
  • -Step S71 H2 O gas flow rate 50 sccm- 200 sccm Processing time: 1 sec to 30 sec -Step S72
  • Flow rate of H2 gas 200 sccm-3000 sccm
  • Ar gas flow rate 100 sccm-6000 sccm Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 20% by volume to 90% by volume
  • Power frequency for plasma generation 40MHz
  • Power for plasma generation 100-600W
  • Processing time 10 sec to 30 sec -Processing conditions common to steps S71 to S72 Processing temperature: 120 ° C. Processing pressure: 266 Pa.
  • step S7 as shown in FIG. 2D, most of the SAM 17 may be decomposed and removed. After step S7, the SAM 17 does not have to remain on the surface 1a of the substrate 1.
  • step S7 may include forming and replenishing SAM17 in the first region A1 on the way.
  • SAM17 hydrofluoric acid can be generated over a long period of time, the width W of an unnecessary portion can be narrowed, and the wiring resistance of the substrate 1 can be reduced. In that case, if O 2 gas or H 2 O gas is supplied before the formation of SAM 17, more SAM 17 can be formed.
  • step S8 of FIG. 1 it is checked whether or not steps S3 to S7 have been executed a set number of times. If the number of executions has not reached the set number of times (steps S8, NO), steps S3 to S7 are executed again. On the other hand, when the number of times of execution has reached the set number of times (step S8, YES), the film thickness of the AlO film has reached the final target film thickness, so the current process is terminated.
  • the number of times of setting in step S8 is set according to the final target film thickness of the AlO film.
  • the number of times of setting in step S8 may be once, but is preferably a plurality of times. If the formation of the AlO film is carried out in a plurality of times, the width W of the unnecessary portion of the target film 18 can be narrowed in each step S6 as compared with the case where the formation of the AlO film is carried out once. The narrower the width W, the easier it is to remove unnecessary parts. Therefore, if the formation of the AlO film is carried out in a plurality of times, the width W of the unnecessary portion of the target film 18 finally obtained can be narrowed as compared with the case where the formation is carried out once, and the wiring resistance of the substrate 1 can be narrowed. Can be reduced.
  • step S3 may be performed after the n (n is a natural number of 1 or more) th step S7 and before the n + 1th step S5.
  • the re-execution of step S3 is effective when the plasmalized H2 gas in step S7 is supplied to the surface 1a of the substrate 1.
  • the surface of the metal film 12 is reduced as in step S2.
  • step S3 is carried out after step S7, the surface of the metal film 12 can be appropriately oxidized. As a result, in the subsequent step S5, a dense SAM 17 can be formed on the surface of the metal film 12.
  • the substrate 1 of this modification further has a fourth region A4 on the surface 1a on which the liner film 14 is exposed.
  • the fourth region A4 is formed between the second region A2 and the third region A3.
  • the liner film 14 is formed on the barrier film 13 and supports the formation of the metal film 12.
  • the metal film 12 is formed on the liner film 14.
  • the liner film 14 is not particularly limited, but is, for example, a Co film or a Ru film.
  • Table 2 summarizes specific examples of the insulating film 11, the metal film 12, the barrier film 13, and the liner film 14.
  • the combination of the insulating film 11, the metal film 12, the barrier film 13, and the liner film 14 is not particularly limited.
  • the raw material of SAM 17 is more easily chemically adsorbed to the liner film 14 than the insulating film 11.
  • step S5 of this modification as shown in FIG. 5B, in the first region A1, the second region A2, the third region A3, and the fourth region A4, the second region A2 and the third region A3 And, the organic compound is selectively chemically adsorbed to the fourth region A4 to form SAM17. SAM17 is not formed in the first region A1.
  • step S6 of this modification as shown in FIG. 5C, SAM17 is used to inhibit the formation of the target film 18 in the second region A2, the third region A3, and the fourth region A4, and the first region A1 is formed.
  • the target film 18 is formed.
  • 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 first region A1.
  • step S7 of this modification as shown in FIG. 5D, a gas containing H 2 O is supplied to the surface 1a of the substrate 1, and an unnecessary portion protruding from the first region A1 of the target film 18 is removed. Etch. Therefore, unnecessary portions of the target film 18 can be selectively removed.
  • the metal film 12 of the substrate 1 of this modification is a cap film.
  • a second metal film 15 made of a metal different from the metal film 12 is embedded in the recess of the insulating film 11.
  • a metal film 12 is formed on the second metal film 15, and the metal film 12 covers the second metal film 15.
  • Table 3 summarizes specific examples of the insulating film 11, the metal film (cap film) 12, the barrier film 13, the liner film 14, and the second metal film 15.
  • the combination of the insulating film 11, the metal film 12, the barrier film 13, the liner film 14, and the second metal film 15 is not particularly limited.
  • step S5 of this modification as shown in FIG. 6B, in the first region A1, the second region A2, the third region A3, and the fourth region A4, the second region A2, the third region A3, and the fourth region A4.
  • the organic compound is selectively chemically adsorbed on the region A4 to form SAM17.
  • SAM17 is not formed in the first region A1.
  • step S6 of this modification as shown in FIG. 6C, SAM17 is used to inhibit the formation of the target film 18 in the second region A2, the third region A3, and the fourth region A4, and the first region A1 is formed.
  • the target film 18 is formed.
  • 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 first region A1.
  • step S7 of this modification as shown in FIG. 6D, a gas containing H 2 O is supplied to the surface 1a of the substrate 1, and an unnecessary portion protruding from the first region A1 of the target film 18 is removed. Etch. Therefore, unnecessary portions of the target film 18 can be selectively removed.
  • the insulating film 11 corresponds to the first film and the metal film 12 corresponds to the second film, but the first film and the second film.
  • the combination of is not particularly limited.
  • Table 4 shows candidates for combinations of the first film, the second film, and the target film 18 when the raw material of SAM 17 is a thiol-based compound.
  • Table 5 shows candidates for combinations of the first film, the second film, and the target film 18 when the raw material of SAM 17 is a phosphonic acid compound.
  • the first film is an insulating film
  • the second film is a conductive film
  • the target film 18 formed on the first film is an insulating film.
  • the film forming apparatus 100 includes a first processing unit 200A, a second processing unit 200B, a third processing unit 200C, a transport unit 400, and a control unit 500.
  • the first processing unit 200A carries out steps S2 to S3 of FIG.
  • the second processing unit 200B carries out steps S4 to S5 of FIG.
  • the third processing unit 200C carries out steps S6 to S7 of FIG.
  • the first processing unit 200A, the second processing unit 200B, and the third processing unit 200C have similar structures. Therefore, it is possible to carry out all of steps S2 to S7 in FIG. 1 only by the first processing unit 200A.
  • the transport unit 400 transports the substrate 1 to the first processing unit 200A, the second processing unit 200B, and the third processing unit 200C.
  • the control unit 500 controls the first processing unit 200A, the second processing unit 200B, the third processing unit 200C, and the transport unit 400.
  • the transport unit 400 has a first transport chamber 401 and a first transport mechanism 402.
  • the internal atmosphere of the first transport chamber 401 is an atmospheric atmosphere.
  • a first transport mechanism 402 is provided inside the first transport chamber 401.
  • the first transport mechanism 402 includes an arm 403 that holds the substrate 1 and travels along the rail 404.
  • the rail 404 extends in the arrangement direction of the carriers C.
  • the transport unit 400 has a second transport chamber 411 and a second transport mechanism 412.
  • the internal atmosphere of the second transport chamber 411 is a vacuum atmosphere.
  • a second transport mechanism 412 is provided inside the second transport chamber 411.
  • the second transfer mechanism 412 includes an arm 413 that holds the substrate 1, and the arm 413 is arranged so as to be movable in the vertical direction and the horizontal direction and rotatably around the vertical axis.
  • the first processing unit 200A, the second processing unit 200B, and the third processing unit 200C are connected to the second transfer chamber 411 via different gate valves G.
  • the transport unit 400 has a load lock chamber 421 between the first transport chamber 401 and the second transport 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).
  • a pressure regulating mechanism not shown
  • a gate valve G is provided between the first transport chamber 401 and the load lock chamber 421, and between the second transport chamber 411 and the load lock chamber 421.
  • the control unit 500 is, for example, a computer, and has a CPU (Central Processing Unit) 501 and a storage medium 502 such as a memory.
  • the storage medium 502 stores programs that control various processes executed by the film forming apparatus 100.
  • the control unit 500 controls the operation of the film forming apparatus 100 by causing the CPU 501 to execute the program 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, and the transport unit 400, and implements the above film forming method.
  • the first transport mechanism 402 takes out the substrate 1 from the carrier C, conveys the taken out substrate 1 to the load lock chamber 421, and exits from the load lock chamber 421.
  • the internal atmosphere of the load lock chamber 421 is switched from the atmospheric atmosphere to the vacuum atmosphere.
  • the second transfer mechanism 412 takes out the substrate 1 from the load lock chamber 421 and conveys the taken out substrate 1 to the first processing unit 200A.
  • the first processing unit 200A carries out steps S2 to S3.
  • the second transfer mechanism 412 takes out the substrate 1 from the first processing unit 200A and conveys the taken out substrate 1 to the second processing unit 200B.
  • the surrounding atmosphere of the substrate 1 can be maintained in a vacuum atmosphere, and oxidation of the substrate 1 can be suppressed.
  • the second processing unit 200B carries out steps S4 to S5.
  • the second transfer mechanism 412 takes out the substrate 1 from the second processing unit 200B, and conveys the taken out substrate 1 to the third processing unit 200C.
  • the surrounding atmosphere of the substrate 1 can be maintained in a vacuum atmosphere, and deterioration of the block performance of the SAM 17 can be suppressed.
  • the third processing unit 200C carries out steps S6 to S7. Subsequently, the control unit 500 checks whether or not steps S3 to S7 have been executed a set number of times. When the number of implementations has not reached the set number of times, the second transfer mechanism 412 takes out the substrate 1 from the third processing unit 200C and conveys the taken out substrate 1 to the first processing unit 200A. After that, the control unit 500 controls the first processing unit 200A, the second processing unit 200B, the third processing unit 200C, and the transport unit 400, and carries out steps S3 to S7.
  • the second transfer mechanism 412 takes out the substrate 1 from the third processing unit 200C, conveys the taken out substrate 1 to the load lock chamber 421, and exits from the load lock chamber 421. do. Subsequently, the internal atmosphere of the load lock chamber 421 is switched from the vacuum atmosphere to the atmospheric atmosphere. After that, the first transfer mechanism 402 takes out the substrate 1 from the load lock chamber 421 and accommodates the taken out substrate 1 in the carrier C. Then, the processing of the substrate 1 is completed.
  • the first processing unit 200A will be described with reference to FIG. Since the second processing unit 200B and the third processing unit 200C are configured in the same manner as the first processing unit 200A, illustration and description thereof will be omitted.
  • 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, for example, a substantially cylindrical shape that projects downward.
  • An exhaust pipe 212 is connected to the exhaust chamber 211, for example, on the side surface of the exhaust chamber 211.
  • the exhaust source 272 is connected to the exhaust pipe 212 via the pressure controller 271.
  • the pressure controller 271 includes a pressure adjusting valve such as a butterfly valve.
  • the exhaust pipe 212 is configured so that the inside of the processing container 210 can be depressurized by the exhaust source 272.
  • the pressure controller 271 and the exhaust source 272 form a gas discharge mechanism 270 that discharges the gas in the processing container 210.
  • a transport port 215 is provided on the side surface of the processing container 210.
  • the transport port 215 is opened and closed by the gate valve G.
  • the loading and unloading of the substrate 1 between the inside of the processing container 210 and the second transport chamber 411 (see FIG. 7) is performed via the transport port 215.
  • a stage 220 which is a holding portion for holding the substrate 1, is provided in the processing container 210.
  • the stage 220 holds the substrate 1 horizontally with the surface 1a of the substrate 1 facing up.
  • the stage 220 is formed in a substantially circular shape in a plan view, and is supported by the support member 221.
  • On the surface of the stage 220 for example, a substantially circular recess 222 for mounting the substrate 1 having a diameter of 300 mm is formed.
  • the recess 222 has an inner diameter slightly larger than the diameter of the substrate 1.
  • the depth of the recess 222 is configured to be substantially the same as, for example, the thickness of the substrate 1.
  • the stage 220 is made of a ceramic material such as aluminum nitride (AlN). Further, the stage 220 may be formed of a metal material such as nickel (Ni).
  • a guide ring for guiding the substrate 1 may be provided on the peripheral edge of the surface of the stage 220.
  • a grounded lower electrode 223 is embedded in the stage 220.
  • a heating mechanism 224 is embedded below the lower electrode 223.
  • the heating mechanism 224 heats the substrate 1 mounted on the stage 220 to a set temperature by supplying power from a power supply unit (not shown) based on a control signal from the control unit 500 (see FIG. 7).
  • the entire stage 220 is made of metal, the entire stage 220 functions as a lower electrode, so that the lower electrode 223 does not have to be embedded in the stage 220.
  • the stage 220 is provided with a plurality of (for example, three) elevating pins 231 for holding and elevating the substrate 1 mounted on the stage 220.
  • the material of the elevating pin 231 may be, for example, ceramics such as alumina (Al 2 O 3 ), quartz, or the like.
  • the lower end of the elevating pin 231 is attached to the support plate 232.
  • the support plate 232 is connected to an elevating mechanism 234 provided outside the processing container 210 via an elevating shaft 233.
  • the elevating mechanism 234 is installed at the lower part of the exhaust chamber 211, for example.
  • the bellows 235 is provided between the opening 219 for the elevating shaft 233 formed on the lower surface of the exhaust chamber 211 and the elevating mechanism 234.
  • the shape of the support plate 232 may be a shape that can be raised and lowered without interfering with the support member 221 of the stage 220.
  • the elevating pin 231 is vertically configured by the elevating mechanism 234 between above the surface of the stage 220 and below the surface of the stage 220.
  • the top wall 217 of the processing container 210 is provided with a gas supply unit 240 via an insulating member 218.
  • the gas supply unit 240 forms an 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.
  • the plasma generation unit 250 that generates plasma includes a matching unit 251 and a high frequency power supply 252.
  • the plasma generation unit 250 is not limited to capacitively coupled plasma, and may generate other plasma such as inductively coupled plasma.
  • the gas supply unit 240 includes a hollow gas supply chamber 241. On the lower surface of the gas supply chamber 241, for example, a large number of holes 242 for dispersing and supplying the processing gas into the processing container 210 are evenly arranged.
  • a heating mechanism 243 is embedded above, for example, the gas supply chamber 241 in the gas supply unit 240. The heating mechanism 243 is heated to a set temperature by supplying power from a power supply unit (not shown) based on a control signal from the control unit 500.
  • a gas supply mechanism 260 is connected to the gas supply chamber 241 via a gas supply path 261.
  • the gas supply mechanism 260 supplies the gas used in at least one of steps S2 to S7 of FIG. 1 to the gas supply chamber 241 via the gas supply path 261.
  • the gas supply mechanism 260 includes individual pipes, an on-off valve provided in the middle of the individual pipes, and a flow rate controller provided in the middle of the individual pipes for each type of gas, although not shown.
  • the on-off valve opens the individual pipe, gas is supplied from the supply source to the gas supply path 261.
  • the supply amount is controlled by the flow rate controller.
  • the on-off valve closes the individual pipe, the supply of gas from the supply source to the gas supply path 261 is stopped.
  • Example 1 the substrate 1 shown in FIG. 2A was prepared.
  • the base substrate 10 was a silicon wafer
  • the insulating film 11 was a SiOC film
  • the metal film 12 was a Cu film
  • the barrier film 13 was a TaN film.
  • the width of the trench was 20 nm and the pitch of the trench was 40 nm.
  • the film forming method shown in FIG. 1 was carried out under the following conditions.
  • the raw material of SAM 17 was PFOT
  • the target film 18 was an AlO film having a film thickness of 5.6 nm.
  • Step S8 in FIG. 1 was set once, and steps S3 to S7 were performed only once.
  • step S2 The processing conditions in step S2 were as follows. H2 gas flow rate: 1000 sccm Ar gas flow rate: 750 sccm Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 57% by volume Power frequency for plasma generation: 40MHz Power for plasma generation: 200W Processing time: 30 sec Processing temperature: 120 ° C Processing pressure: 266 Pa.
  • step S3 The processing conditions in step S3 were as follows. O 2 gas flow rate: 1000 sccm Processing time: 900 sec Processing temperature: 120 ° C Processing pressure: 266 Pa.
  • step S4 The processing conditions in step S4 were as follows. IPA gas flow rate: 100 sccm Processing time: 900 sec Processing temperature: 150 ° C Processing pressure: 360 Pa.
  • step S5 The processing conditions in step S5 were as follows. PFOT gas flow rate: 100 sccm Processing time: 600 sec Processing temperature: 150 ° C Processing pressure: 620 Pa.
  • step S6 The processing conditions in step S6 were as follows. -Step S61 TMA gas flow rate: 50 sccm Processing time: 0.1 sec -Step S62 Ar gas flow rate: 6000 sccm Processing time: 1 sec -Step S63 H2 O gas flow rate: 100 sccm Processing time: 1 sec -Step S64 Ar gas flow rate: 6000 sccm Processing time: 2 sec -Processing conditions common to steps S61 to S64 Processing temperature: 120 ° C. Processing pressure: 400Pa The number of times of setting step S65 in FIG. 3 was 68 times, and steps S61 to S64 were repeated 68 times.
  • step S7 The processing conditions in step S7 were as follows. -Step S71 H2 O gas flow rate: 100 sccm Processing time: 2 sec -Step S72 H 2 gas flow rate: 2000 sccm Ar gas flow rate: 3000 sccm Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 40% by volume Power frequency for plasma generation: 40MHz Power for plasma generation: 200W Processing time: 10 sec -Processing conditions common to steps S71 to S72 Processing temperature: 120 ° C. Processing pressure: 266Pa The number of times of setting step S73 in FIG. 4 was 30 times, and steps S71 to S72 were repeated 30 times.
  • the film thickness of the AlO film, which is the target film 18, was 5.6 nm, and the width W of the unnecessary portion (see FIG. 2C) was 6.2 nm.
  • the film thickness and width W were measured using an SEM photograph of the cross section of the substrate.
  • the width W of the unnecessary portion was 4.7 nm. Therefore, it was found that the width W of the unnecessary portion was narrowed by 1.5 nm by step S7.
  • Example 2 the same substrate 1 as in Example 1 was prepared, and the film forming method shown in FIG. 1 was carried out under the following conditions.
  • the main differences between Example 2 and Example 1 are (1) the number of times step S8 in FIG. 1 is set to 2 times, and (2) the number of times step S65 in FIG. 3 is set to 45 times. That is, (3) the number of times of setting in step S73 in FIG. 4 is set to 10 times. In Example 2, step S4 was not performed.
  • step S2 The processing conditions in step S2 were as follows. H 2 gas flow rate: 2000 sccm Ar gas flow rate: 3000 sccm Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 40% by volume Power frequency for plasma generation: 40MHz Power for plasma generation: 200W Processing time: 10 sec Processing temperature: 120 ° C Processing pressure: 266 Pa.
  • step S3 The processing conditions in step S3 were as follows. O 2 gas flow rate: 1000 sccm Processing time: 600 sec Processing temperature: 120 ° C Processing pressure: 266 Pa.
  • step S5 The processing conditions in step S5 were as follows. PFOT gas flow rate: 100 sccm Processing time: 300 sec Processing temperature: 150 ° C Processing pressure: 620 Pa.
  • step S6 The processing conditions in step S6 were as follows. -Step S61 TMA gas flow rate: 50 sccm Processing time: 0.1 sec -Step S62 Ar gas flow rate: 6000 sccm Processing time: 1 sec -Step S63 H2 O gas flow rate: 100 sccm Processing time: 1 sec -Step S64 Ar gas flow rate: 6000 sccm Processing time: 2 sec -Processing conditions common to steps S61 to S64 Processing temperature: 120 ° C. Processing pressure: 400Pa The number of times of setting step S65 in FIG. 3 was 45 times, and steps S61 to S64 were repeated 45 times.
  • step S7 The processing conditions in step S7 were as follows. -Step S71 H2 O gas flow rate: 100 sccm Processing time: 2 sec -Step S72 H 2 gas flow rate: 2000 sccm Ar gas flow rate: 3000 sccm Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 40% by volume Power frequency for plasma generation: 40MHz Power for plasma generation: 200W Processing time: 20 sec -Processing conditions common to steps S71 to S72 Processing temperature: 120 ° C. Processing pressure: 266Pa The number of times of setting step S73 in FIG. 4 was 10, and steps S71 to S72 were repeated 10 times.
  • the main differences between the second embodiment and the first embodiment are that (1) the number of times the step S8 in FIG. 1 is set is set to two, and (2) the number of times the step S65 in FIG. 3 is set is 45. It was set to 10 times, and (3) the number of times of setting in step S73 in FIG. 4 was set to 10 times.
  • Example 2 after the completion of all the treatments, the film thickness of the AlO film, which is the target film 18, was 6.0 nm, and the width W of the unnecessary portion was 1.0 nm.
  • Example 2 when the final target film thickness of the AlO film is about the same, the set number of steps S8 in FIG. 1 is set to a plurality of times, and the formation of the AlO film is carried out in a plurality of times. Then, it can be seen that the width W of the unnecessary portion can be narrowed as compared with the case where the implementation is performed once.
  • Example 3 In Example 3, the same as in Example 2, except that the processing time of step S72 in FIG. 4 is set to 30 sec and the number of times of setting step S73 in FIG. 4 is set to 3, it is shown in FIG. The film forming method was carried out.
  • Example 3 after the completion of all the treatments, the film thickness of the AlO film, which is the target film 18, was 6.0 nm, and the width W of the unnecessary portion was 0.9 nm. Therefore, in Example 3, the same result as in Example 2 was obtained.
  • Example 4 the film forming method shown in FIG. 1 was carried out in the same manner as in Example 2, except that the processing time of step S3 in FIG. 1 was set to 300 sec. In Example 2, as described above, the processing time of step S3 in FIG. 1 was 600 sec.
  • Example 4 after the completion of all the treatments, the film thickness of the AlO film, which is the target film 18, was 6.2 nm, and the width W of the unnecessary portion was 3.9 nm.
  • Example 2 as described above, after the completion of all the treatments, the film thickness of the AlO film, which is the target film 18, was 6.0 nm, and the width W of the unnecessary portion was 1.0 nm.
  • step S3 From Example 4 and Example 2, it can be seen that if the processing time of step S3 is extended from 300 sec to 600 sec, the width W of the unnecessary portion becomes narrower after the completion of all the processing. It is presumed that if the treatment time in step S3 is long to some extent and the surface of the Cu film is oxidized to some extent, a dense SAM can be obtained and hydrofluoric acid is produced over a long period of time in step S7.
  • Example 5 the substrate 1 was treated under the same conditions as in Example 2 except that the width of the trench on the surface of the SiOC film was changed to 50 nm and the pitch of the trench was changed to 100 nm.
  • Example 5 after the completion of all the treatments, the film thickness of the AlO film, which is the target film 18, was 6.4 nm, and the width W of the unnecessary portion was 0.0 nm.
  • FIG. 9 shows an SEM photograph of a cross section of the substrate obtained in Example 5. As is clear from FIG. 9, no protrusion of the AlO film was observed.
  • Substrate 1a Surface 11 Insulation film (first film) 12 Metal film (second film) 17 SAM (Self-assembled monolayer) 18 Target film A1 1st region A2 2nd region

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Abstract

This film deposition method includes (A)-(D) below. (A) Preparing a substrate having, on a surface thereof, a first region on which a first film is exposed and a second region on which a second film formed from a material different from that for the first film is exposed. (B) Supplying a fluorine-containing organic compound, which is a source material for a self-assembled monolayer film, onto the surface of the substrate to selectively form the self-assembled monolayer film on the second region among the first region and the second region. (C) Forming a desired film on the first region using the self-assembled monolayer film while inhibiting the formation of the desired film on the second region. (D) Supplying a gas containing H2O to the surface of the substrate to etch an edge portion that protrudes from the first region in the desired film.

Description

成膜方法及び成膜装置Film formation method and film formation equipment
　本開示は、成膜方法及び成膜装置に関する。 This disclosure relates to a film forming method and a film forming apparatus.
　特許文献１、２には、自己組織化単分子膜（Ｓｅｌｆ－Ａｓｓｅｍｂｌｅｄ　Ｍｏｎｏｌａｙｅｒ：ＳＡＭ）を用いて基板表面の一部における対象膜の形成を阻害しつつ、基板表面の残部に対象膜を形成する技術が記載されている。 In Patent Documents 1 and 2, a self-assembled monolayer (SELf-Assembled Monolayer: SAM) is used to form a target film on the rest of the substrate surface while inhibiting the formation of the target film on a part of the substrate surface. The technology is described.
　非特許文献１には、酸化アルミニウム膜の表面に対してフッ酸とＴＭＡ（トリメチルアルミニウム）とを交互に供給し、酸化アルミニウム膜の表面をエッチングする、原子層エッチング（Ａｔｏｍｉｃ　Ｌａｙｅｒ　Ｅｔｃｈｉｎｇ：ＡＬＥ）が記載されている。 Non-Patent Document 1 describes atomic layer etching (ALE) in which hydrofluoric acid and TMA (trimethylaluminum) are alternately supplied to the surface of an aluminum oxide film to etch the surface of the aluminum oxide film. Have been described.
日本国特表２０１０－５４０７７３号公報Japan Special Table 2010-540773 Gazette 日本国特表２０１３－５２００２８号公報Japan Special Table 2013-520028 Gazette
　本開示の一態様は、ＳＡＭを用いて対象膜の形成を阻害した後、対象膜の不要な部位を選択的に除去する、技術を提供する。 One aspect of the present disclosure provides a technique for inhibiting the formation of a target membrane using SAM and then selectively removing an unnecessary portion of the target membrane.
　本開示の一態様の成膜方法は、下記（Ａ）～（Ｄ）を含む。（Ａ）第１膜が露出する第１領域と、前記第１膜とは異なる材料で形成される第２膜が露出する第２領域とを表面に有する基板を準備する。（Ｂ）前記基板の前記表面に対して自己組織化単分子膜の原料であるフッ素を含む有機化合物を供給し、前記第１領域及び前記第２領域の中で、前記第２領域に選択的に、前記自己組織化単分子膜を形成する。（Ｃ）前記自己組織化単分子膜を用い前記第２領域における対象膜の形成を阻害ししつつ、前記第１領域に前記対象膜を形成する。（Ｄ）前記基板の前記表面に対してＨ２Ｏを含むガスを供給し、前記対象膜の前記第１領域からはみ出した端部をエッチングする。 The film forming method of one aspect of the present disclosure includes the following (A) to (D). (A) A substrate having a first region on which the first film is exposed and a second region on which the second film formed of a material different from the first film is exposed is prepared. (B) An organic compound containing fluorine, which is a raw material for a self-assembled monolayer, is supplied to the surface of the substrate, and the second region is selectively selected among the first region and the second region. To form the self-assembled monolayer. (C) Using the self-assembled monolayer, the target membrane is formed in the first region while inhibiting the formation of the target membrane in the second region. (D) A gas containing H2O is supplied to the surface of the substrate, and the end portion of the target film protruding from the first region is etched.
　本開示の一態様によれば、ＳＡＭを用いて対象膜の形成を阻害した後、対象膜の不要な部位を選択的に除去できる。 According to one aspect of the present disclosure, after inhibiting the formation of the target membrane using SAM, unnecessary parts of the target membrane can be selectively removed.
図１は、一実施形態に係る成膜方法を示すフローチャートである。FIG. 1 is a flowchart showing a film forming method according to an embodiment. 図２Ａは、一実施形態に係る基板のステップＳ１を示す図である。FIG. 2A is a diagram showing step S1 of the substrate according to the embodiment. 図２Ｂは、一実施形態に係る基板のステップＳ５を示す図である。FIG. 2B is a diagram showing step S5 of the substrate according to the embodiment. 図２Ｃは、一実施形態に係る基板のステップＳ６を示す図である。FIG. 2C is a diagram showing step S6 of the substrate according to the embodiment. 図２Ｄは、一実施形態に係る基板のステップＳ７の一例を示す図である。FIG. 2D is a diagram showing an example of step S7 of the substrate according to the embodiment. 図３は、ステップＳ６のサブルーチンの一例を示すフローチャートである。FIG. 3 is a flowchart showing an example of the subroutine in step S6. 図４は、ステップＳ７のサブルーチンの一例を示すフローチャートである。FIG. 4 is a flowchart showing an example of the subroutine in step S7. 図５Ａは、第１変形例に係る基板のステップＳ１を示す図である。FIG. 5A is a diagram showing step S1 of the substrate according to the first modification. 図５Ｂは、第１変形例に係る基板のステップＳ５を示す図である。FIG. 5B is a diagram showing step S5 of the substrate according to the first modification. 図５Ｃは、第１変形例に係る基板のステップＳ６を示す図である。FIG. 5C is a diagram showing step S6 of the substrate according to the first modification. 図５Ｄは、第１変形例に係る基板のステップＳ７の一例を示す図である。FIG. 5D is a diagram showing an example of step S7 of the substrate according to the first modification. 図６Ａは、第２変形例に係る基板のステップＳ１を示す図である。FIG. 6A is a diagram showing step S1 of the substrate according to the second modification. 図６Ｂは、第２変形例に係る基板のステップＳ５を示す図である。FIG. 6B is a diagram showing step S5 of the substrate according to the second modification. 図６Ｃは、第２変形例に係る基板のステップＳ６を示す図である。FIG. 6C is a diagram showing step S6 of the substrate according to the second modification. 図６Ｄは、第２変形例に係る基板のステップＳ７の一例を示す図である。FIG. 6D is a diagram showing an example of step S7 of the substrate according to the second modification. 図７は、一実施形態に係る成膜装置を示す平面図である。FIG. 7 is a plan view showing a film forming apparatus according to an embodiment. 図８は、図７の第１処理部の一例を示す断面図である。FIG. 8 is a cross-sectional view showing an example of the first processing unit of FIG. 7. 図９は、実施例５で得られた基板の断面のＳＥＭ写真である。FIG. 9 is an SEM photograph of a cross section of the substrate obtained in Example 5.
　以下、本開示の実施形態について図面を参照して説明する。なお、各図面において同一の又は対応する構成には同一の符号を付し、説明を省略することがある。 Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In each drawing, the same or corresponding configurations may be designated by the same reference numerals and description thereof may be omitted.
　先ず、図１及び図２Ａ～図２Ｄを参照して、本実施形態に係る成膜方法について説明する。成膜方法は、例えば図１に示すステップＳ１～Ｓ８を含む。なお、成膜方法は、少なくともステップＳ１、Ｓ５～Ｓ８を含めばよく、例えばステップＳ２～Ｓ４を含まなくてもよい。また、成膜方法は、図１に示すステップＳ１～Ｓ８以外のステップを含んでもよい。 First, the film forming method according to the present embodiment will be described with reference to FIGS. 1 and 2A to 2D. The film forming method includes, for example, steps S1 to S8 shown in FIG. The film forming method may include at least steps S1 and S5 to S8, and may not include, for example, steps S2 to S4. Further, the film forming method may include steps other than steps S1 to S8 shown in FIG.
　先ず、図１のステップＳ１では、図２Ａに示すように、基板１を準備する。基板１を準備することは、例えば、図７に示す成膜装置１００にキャリアＣを搬入することを含む。キャリアＣは、複数の基板１を収容する。 First, in step S1 of FIG. 1, the substrate 1 is prepared as shown in FIG. 2A. Preparing the substrate 1 includes, for example, carrying the carrier C into the film forming apparatus 100 shown in FIG. 7. The carrier C accommodates a plurality of substrates 1.
　基板１は、シリコンウェハ又は化合物半導体ウェハ等の下地基板１０を有する。化合物半導体ウェハは、特に限定されないが、例えばＧａＡｓウェハ、ＳｉＣウェハ、ＧａＮウェハ、又はＩｎＰウェハである。 The substrate 1 has a base substrate 10 such as a silicon wafer or a compound semiconductor wafer. The compound semiconductor wafer is not particularly limited, and is, for example, a GaAs wafer, a SiC wafer, a GaN wafer, or an InP wafer.
　基板１は、下地基板１０の上に形成される絶縁膜１１を有する。絶縁膜１１と下地基板１０の間に、導電膜等が形成されてもよい。絶縁膜１１は、例えば層間絶縁膜である。層間絶縁膜は、好ましくは低誘電率（Ｌｏｗ－ｋ）膜である。 The substrate 1 has an insulating film 11 formed on the base substrate 10. A conductive film or the like may be formed between the insulating film 11 and the base substrate 10. The insulating film 11 is, for example, an interlayer insulating film. The interlayer insulating film is preferably a low dielectric constant (Low-k) film.
　絶縁膜１１は、特に限定されないが、例えばＳｉＯ膜、ＳｉＮ膜、ＳｉＯＣ膜、ＳｉＯＮ膜、又はＳｉＯＣＮ膜である。ここで、ＳｉＯ膜とは、シリコン（Ｓｉ）と酸素（Ｏ）を含む膜という意味である。ＳｉＯ膜におけるＳｉとＯの原子比は１：１には限定されない。ＳｉＮ膜、ＳｉＯＣ膜、ＳｉＯＮ膜、及びＳｉＯＣＮ膜について同様である。絶縁膜１１は、基板１の表面１ａに、凹部を有する。凹部は、トレンチ、コンタクトホール又はビアホールである。 The insulating film 11 is not particularly limited, but is, for example, a SiO film, a SiN film, a SiOC 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 not limited to 1: 1. The same applies to the SiN film, the SiOC film, the SiON film, and the SiOCN film. The insulating film 11 has a recess on the surface 1a of the substrate 1. The recess is a trench, contact hole or via hole.
　基板１は、凹部の内部に充填される金属膜１２を有する。金属膜１２は特に限定されないが、例えば、Ｃｕ膜、Ｃｏ膜、Ｒｕ膜、又はＷ膜である。 The substrate 1 has a metal film 12 that is filled inside the recess. The metal film 12 is not particularly limited, but is, for example, a Cu film, a Co film, a Ru film, or a W film.
　基板１は、凹部に沿って形成されるバリア膜１３を更に有する。バリア膜１３は、金属膜１２から絶縁膜１１への金属拡散を抑制する。バリア膜１３は、特に限定されないが、例えば、ＴａＮ膜、又はＴｉＮ膜である。ここで、ＴａＮ膜とは、タンタル（Ｔａ）と窒素（Ｎ）を含む膜という意味である。ＴａＮ膜におけるＴａとＮの原子比は１：１には限定されない。ＴｉＮ膜について同様である。 The substrate 1 further has a barrier membrane 13 formed along the recesses. The barrier film 13 suppresses metal diffusion from the metal 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.
　表１に、絶縁膜１１と、金属膜１２と、バリア膜１３との具体例をまとめて示す。 Table 1 summarizes specific examples of the insulating film 11, the metal film 12, and the barrier film 13.
Figure JPOXMLDOC01-appb-T000001
 　なお、絶縁膜１１と、金属膜１２と、バリア膜１３との組み合わせは、特に限定されない。
Figure JPOXMLDOC01-appb-T000001
 The combination of the insulating film 11, the metal film 12, and the barrier film 13 is not particularly limited.
　図２Ａに示すように、基板１は、その表面１ａに、絶縁膜１１が露出する第１領域Ａ１と、金属膜１２が露出する第２領域Ａ２とを有する。また、基板１は、その表面１ａに、バリア膜１３が露出する第３領域Ａ３を更に有してもよい。第３領域Ａ３は、第１領域Ａ１と第２領域Ａ２の間に形成される。なお、基板１の構造は、後述するように、図２Ａに示す構造には限定されない。 As shown in FIG. 2A, the substrate 1 has a first region A1 in which the insulating film 11 is exposed and a second region A2 in which the metal film 12 is exposed on the surface 1a thereof. Further, the substrate 1 may further have a third region A3 on the surface 1a on which the barrier membrane 13 is exposed. The third region A3 is formed between the first region A1 and the second region A2. The structure of the substrate 1 is not limited to the structure shown in FIG. 2A, as will be described later.
　次に、図１のステップＳ２では、基板１の表面１ａをクリーニングする。例えば、ステップＳ２では、基板１の表面１ａに対してＨ２ガス等の還元性ガスを供給し、基板１の表面１ａに形成される自然酸化膜を除去する。自然酸化膜は、例えば金属膜１２の表面に形成されたものである。還元性ガスは、プラズマ化されてもよい。また、還元性ガスは、Ａｒガス等の希ガスと混合して用いられてもよい。 Next, in step S2 of FIG. 1, the surface 1a of the substrate 1 is cleaned. For example, in step S2, a reducing gas such as H 2 gas is supplied to the surface 1a of the substrate 1 to remove the natural oxide film formed on the surface 1a of the substrate 1. The natural oxide film is formed on the surface of the metal film 12, for example. The reducing gas may be plasmatized. Further, the reducing gas may be used by mixing with a rare gas such as Ar gas.
　ステップＳ２の処理条件の一例を下記に示す。
Ｈ２ガスの流量：５００ｓｃｃｍ～２０００ｓｃｃｍ
Ａｒガスの流量：３００ｓｃｃｍ～６０００ｓｃｃｍ
Ｈ２ガスとＡｒガスの混合ガスに占めるＨ２ガスの割合：３０体積％～９０体積％
プラズマ生成用の電源周波数：４０ＭＨｚ
プラズマ生成用の電力：２００Ｗ
処理時間：１０ｓｅｃ～３０ｓｅｃ
処理温度（基板温度）：１２０℃
処理圧力：２６６Ｐａ。 An example of the processing conditions in step S2 is shown below.
H2 gas flow rate: 500 sccm - 2000 sccm
Ar gas flow rate: 300 sccm-6000 sccm
Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 30% by volume to 90% by volume
Power frequency for plasma generation: 40MHz
Power for plasma generation: 200W
Processing time: 10 sec to 30 sec
Processing temperature (board temperature): 120 ° C
Processing pressure: 266 Pa.
　次に、図１のステップＳ３では、基板１の表面１ａを酸化する。例えば、ステップＳ３では、基板１の表面１ａに対してＯ２ガス等の酸素を含むガスを供給し、金属膜１２の表面を適度に酸化する。事前に自然酸化膜が除去済みであるので、酸素原子の密度が所望の密度になる。その結果、後述のステップＳ５において、金属膜１２の表面に緻密な自己素子化単分子膜（ＳＡＭ）を形成できる。 Next, in step S3 of FIG. 1, the surface 1a of the substrate 1 is oxidized. For example, in step S3, a gas containing oxygen such as O 2 gas is supplied to the surface 1a of the substrate 1 to appropriately oxidize the surface of the metal film 12. Since the natural oxide film has been removed in advance, the density of oxygen atoms becomes the desired density. As a result, in step S5 described later, a dense self-assembled monolayer (SAM) can be formed on the surface of the metal film 12.
　ステップＳ３の処理条件の一例を下記に示す。
Ｏ２ガスの流量：１００ｓｃｃｍ～２０００ｓｃｃｍ
処理時間：３００ｓｅｃ～９００ｓｅｃ（好ましくは６００ｓｅｃ）
処理温度：１２０℃
処理圧力：２００Ｐａ～１２００Ｐａ。 An example of the processing conditions in step S3 is shown below.
O 2 gas flow rate: 100 sccm-2000 sccm
Processing time: 300 sec to 900 sec (preferably 600 sec)
Processing temperature: 120 ° C
Processing pressure: 200 Pa to 1200 Pa.
　次に、図１のステップＳ４では、基板１の表面１ａに対してＩＰＡ（Ｉｓｏｐｒｏｐｙｌ　Ａｌｃｏｈｏｌ）ガスを供給する。ステップＳ４の処理条件の一例を下記に示す。
ＩＰＡガスの流量：１０ｓｃｃｍ～２００ｓｃｃｍ
処理時間：０ｓｅｃ～９００ｓｅｃ
処理温度：１５０℃
処理圧力：３００Ｐａ～４００Ｐａ
処理時間は０ｓｅｃであってもよく、つまり、ステップＳ４は省略されてもよい。 Next, in step S4 of FIG. 1, IPA (isopropanol Alcohol) gas is supplied to the surface 1a of the substrate 1. An example of the processing conditions in step S4 is shown below.
IPA gas flow rate: 10 sccm-200 sccm
Processing time: 0 sec to 900 sec
Processing temperature: 150 ° C
Processing pressure: 300Pa-400Pa
The processing time may be 0 sec, that is, step S4 may be omitted.
　次に、図１のステップＳ５では、基板１の表面１ａに対してＳＡＭ１７の原料であるフッ素を含む有機化合物を供給し、図２Ｂに示すように、第１領域Ａ１及び第２領域Ａ２の中で、第２領域Ａ２に選択的に、ＳＡＭ１７を形成する。ＳＡＭ１７の原料は、特に限定されないが、例えばチオール系化合物である。 Next, in step S5 of FIG. 1, an organic compound containing fluorine, which is a raw material of SAM 17, is supplied to the surface 1a of the substrate 1, and as shown in FIG. 2B, in the first region A1 and the second region A2. Then, SAM17 is selectively formed in the second region A2. The raw material of SAM17 is not particularly limited, but is, for example, a thiol-based compound.
　チオール系化合物は、水素化された硫黄を頭部基に有し、一般式「Ｒ－ＳＨ」で表される。Ｒは、例えば、炭化水素基の水素の少なくとも一部をフッ素に置換したものである。チオール系化合物の具体例として、ＣＦ３（ＣＦ２）５ＣＨ２ＣＨ２ＳＨ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロオクタンチオール：ＰＦＯＴ）、及びＣＦ３（ＣＦ２）７ＣＨ２ＣＨ２ＳＨ（１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロデカンチオール：ＰＦＤＴ）が挙げられる。 The thiol-based compound has hydrogenated sulfur in the head group and is represented by the general formula "R-SH". R is, for example, a hydrocarbon group in which at least a part of hydrogen is replaced with fluorine. Specific examples of thiol compounds include CF 3 (CF 2 ) 5 CH 2 CH 2 SH (1H, 1H, 2H, 2H-perfluorooctane thiol: PFOT), and CF 3 (CF 2 ) 7 CH 2 CH 2 SH. (1H, 1H, 2H, 2H-perfluorodecanethiol: PFDT) can be mentioned.
　チオール系化合物は、絶縁膜に比べて導電膜に化学吸着しやすい。第１領域Ａ１に絶縁膜１１が露出し、第２領域Ａ２に金属膜１２が露出する場合、第１領域Ａ１及び第２領域Ａ２の中で、第２領域Ａ２に選択的に、ＳＡＭ１７が形成される。 Thiol compounds are more easily chemisorbed on the conductive film than the insulating film. When the insulating film 11 is exposed in the first region A1 and the metal film 12 is exposed in the second region A2, the SAM 17 is selectively formed in the second region A2 in the first region A1 and the second region A2. Will be done.
　チオール系化合物の化学吸着する導電膜としては、金属膜の他に、ＴａＮ膜等の窒化膜も挙げられる。従って、ＳＡＭ１７は、第２領域Ａ２の他に、第３領域Ａ３にも形成される。但し、チオール系化合物は、窒化膜よりも金属膜に化学吸着しやすい。従って、ＳＡＭ１７は、第３領域Ａ３よりも第２領域Ａ２に形成されやすい。 Examples of the conductive film that chemically adsorbs a thiol compound include a nitride film such as a TaN film in addition to a metal film. Therefore, the SAM 17 is formed not only in the second region A2 but also in the third region A3. However, the thiol compound is more easily chemically adsorbed to the metal film than the nitride film. Therefore, the SAM 17 is more likely to be formed in the second region A2 than in the third region A3.
　なお、ＳＡＭ１７の原料は、チオール系化合物には限定されない。例えば、ＳＡＭ１７の原料は、ホスホン酸系化合物であってもよい。ホスホン酸系化合物は、一般式「Ｒ－Ｐ（＝Ｏ）（ＯＨ）２」で表される。Ｒは、例えば、炭化水素基の水素の少なくとも一部をフッ素に置換したものである。 The raw material of SAM17 is not limited to thiol compounds. For example, the raw material of SAM17 may be a phosphonic acid-based compound. The phosphonic acid compound is represented by the general formula "RP (= O) (OH) 2 ". R is, for example, a hydrocarbon group in which at least a part of hydrogen is replaced with fluorine.
　ステップＳ５の処理条件の一例を下記に示す。
ＰＦＯＴガスの流量：８０ｓｃｃｍ～２００ｓｃｃｍ
処理時間：９０ｓｅｃ～９００ｓｅｃ（好ましくは３００ｓｅｃ）
処理温度：１５０℃
処理圧力：２００Ｐａ～４０００Ｐａ。 An example of the processing conditions in step S5 is shown below.
PFOT gas flow rate: 80 sccm-200 sccm
Processing time: 90 sec to 900 sec (preferably 300 sec)
Processing temperature: 150 ° C
Processing pressure: 200Pa-4000Pa.
　次に、図１のステップＳ６では、図２Ｃに示すように、ＳＡＭ１７を用い第２領域Ａ２における対象膜１８の形成を阻害しつつ、第１領域Ａ１に対象膜１８を形成する。対象膜１８は、例えば絶縁膜であり、絶縁膜１１の上に形成される。 Next, in step S6 of FIG. 1, as shown in FIG. 2C, the target film 18 is formed in the first region A1 while inhibiting the formation of the target film 18 in the second region A2 using SAM17. The target film 18 is, for example, an insulating film, and is formed on the insulating film 11.
　ＳＡＭ１７は、上記の通り、第２領域Ａ２だけではなく、第３領域Ａ３にも形成される。この場合、ステップＳ６では、ＳＡＭ１７を用い第２領域Ａ２及び第３領域Ａ３における対象膜１８の形成を阻害しつつ、第１領域Ａ１に対象膜１８を形成する。 As described above, the SAM 17 is formed not only in the second region A2 but also in the third region A3. In this case, in step S6, the target film 18 is formed in the first region A1 while inhibiting the formation of the target film 18 in the second region A2 and the third region A3 using the SAM 17.
　対象膜１８は、特に限定されないが、例えばＡｌＯ膜、ＳｉＯ膜、ＳｉＮ膜、ＺｒＯ膜、又はＨｆＯ膜等である。ここで、ＡｌＯ膜とは、アルミニウム（Ａｌ）と酸素（Ｏ）を含む膜という意味である。ＡｌＯ膜におけるＡｌとＯの原子比は１：１には限定されない。ＳｉＯ膜、ＳｉＮ膜、ＺｒＯ膜、及びＨｆＯ膜について同様である。対象膜１８は、ＣＶＤ（Ｃｈｅｍｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）法、又はＡＬＤ（Ａｔｏｍｏｉｃ　Ｌａｙｅｒ　Ｄｅｐｏｓｉｔｉｏｎ）法で形成される。 The target film 18 is not particularly limited, but is, for example, an AlO film, a SiO film, a SiN film, a ZrO film, an HfO film, or the like. Here, the AlO film means a film containing aluminum (Al) and oxygen (O). The atomic ratio of Al to O in the AlO film is not limited to 1: 1. The same applies to the SiO film, SiN film, ZrO film, and HfO film. The target film 18 is formed by a CVD (Chemical Vapor Deposition) method or an ALD (Atomic Layer Deposition) method.
　ＡｌＯ膜をＡＬＤ法で形成する場合、ＴＭＡ（トリメチルアルミニウム）ガスなどのＡｌ含有ガスと、水蒸気（Ｈ２Ｏガス）などの酸化ガスとが、基板１の表面１ａに対して交互に供給される。ＡｌＯ膜の成膜方法は、例えば図３に示すステップＳ６１～Ｓ６５を含む。 When the AlO film is formed by the ALD method, an Al-containing gas such as TMA (trimethylaluminum) gas and an oxidizing gas such as water vapor ( H2O gas) are alternately supplied to the surface 1a of the substrate 1. .. The method for forming an AlO film includes, for example, steps S61 to S65 shown in FIG.
　先ず、ステップＳ６１では、基板１の表面１ａに対してＡｌ含有ガスを供給する。次に、ステップＳ６２では、基板１の表面１ａに対してＡｒガス等の不活性ガスを供給し、基板１の表面１ａに化学吸着しなかった余剰のＡｌ含有ガスをパージする。次に、ステップＳ６３では、基板１の表面１ａに対して酸化ガスを供給する。次に、ステップＳ６４では、基板１の表面１ａに対してＡｒガス等の不活性ガスを供給し、基板１の表面１ａに化学吸着しなかった余剰の酸化ガスをパージする。なお、ステップＳ６１とステップＳ６３の順番は逆でもよい。 First, in step S61, the Al-containing gas is supplied to the surface 1a of the substrate 1. Next, in step S62, an inert gas such as Ar gas is supplied to the surface 1a of the substrate 1 to purge the excess Al-containing gas that has not been chemically adsorbed on the surface 1a of the substrate 1. Next, in step S63, the oxidation gas is supplied to the surface 1a of the substrate 1. Next, in step S64, an inert gas such as Ar gas is supplied to the surface 1a of the substrate 1 to purge the excess oxidizing gas that has not been chemically adsorbed on the surface 1a of the substrate 1. The order of steps S61 and S63 may be reversed.
　次に、ステップＳ６５では、ステップＳ６１～Ｓ６４を設定回数実施したか否かをチェックする。実施回数が設定回数に達していない場合（ステップＳ６５、ＮＯ）、ステップＳ６１～Ｓ６４を再度実施する。一方、実施回数が設定回数に達している場合（ステップＳ６５、ＹＥＳ）、ＡｌＯ膜の膜厚が目標膜厚に達しているので、今回の処理を終了する。ステップＳ６５の設定回数は、ＡｌＯ膜の目標膜厚に応じて設定されるが、例えば２０回～８０回である。 Next, in step S65, it is checked whether or not steps S61 to S64 have been executed a set number of times. If the number of executions has not reached the set number of times (steps S65, NO), steps S61 to S64 are executed again. On the other hand, when the number of times of implementation has reached the set number of times (step S65, YES), the film thickness of the AlO film has reached the target film thickness, so the current process is terminated. The number of times of setting in step S65 is set according to the target film thickness of the AlO film, and is, for example, 20 to 80 times.
　ステップＳ６の処理条件の一例を下記に示す。
・ステップＳ６１
ＴＭＡガスの流量：５０ｓｃｃｍ
処理時間：０．１ｓｅｃ～２ｓｅｃ
・ステップＳ６２
Ａｒガスの流量：１０００ｓｃｃｍ～８０００ｓｃｃｍ
処理時間：０．５ｓｅｃ～２ｓｅｃ
・ステップＳ６３
Ｈ２Ｏガスの流量：５０ｓｃｃｍ～２００ｓｃｃｍ
処理時間：０．５ｓｅｃ～２ｓｅｃ
・ステップＳ６４
Ａｒガスの流量：１０００ｓｃｃｍ～８０００ｓｃｃｍ
処理時間：０．５ｓｅｃ～５ｓｅｃ
・ステップＳ６１～Ｓ６４に共通の処理条件
処理温度：１００℃～２５０℃
処理圧力：１３３Ｐａ～１２００Ｐａ。 An example of the processing conditions in step S6 is shown below.
-Step S61
TMA gas flow rate: 50 sccm
Processing time: 0.1 sec to 2 sec
-Step S62
Ar gas flow rate: 1000 sccm-8000 sccm
Processing time: 0.5 sec to 2 sec
-Step S63
H2 O gas flow rate: 50 sccm- 200 sccm
Processing time: 0.5 sec to 2 sec
-Step S64
Ar gas flow rate: 1000 sccm-8000 sccm
Processing time: 0.5 sec to 5 sec
-Processing conditions common to steps S61 to S64 Processing temperature: 100 ° C to 250 ° C
Processing pressure: 133 Pa to 1200 Pa.
　ところで、図２Ｃに示すように、ＳＡＭ１７は対象膜１８の形成を阻害するが、ＳＡＭ１７のブロック性能は完全ではなく、対象膜１８は第１領域Ａ１から横にはみ出してしまう。そのはみ出した部位、つまり、不要な部位の幅Ｗは、例えば２ｎｍ～１０ｎｍ程度である。 By the way, as shown in FIG. 2C, 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 first region A1. The width W of the protruding portion, that is, the unnecessary portion is, for example, about 2 nm to 10 nm.
　そこで、ステップＳ７では、基板１の表面１ａに対してＨ２Ｏを含むガスを供給する。Ｈ２Ｏを含むガスと、ＳＡＭ１７との反応によって、フッ酸が生成する。生成したフッ酸によって、図２Ｄに示すように、対象膜１８をエッチングすることができる。エッチングにより生じる生成物は、揮発性であり、気化し、排気される。対象膜１８は、上記の通り、例えばＡｌＯ膜、ＳｉＯ膜、ＳｉＮ膜、ＺｒＯ膜、又はＨｆＯ膜等である。これらの膜は、いずれも、フッ酸によってエッチング可能である。 Therefore, in step S7, a gas containing H2O is supplied to the surface 1a of the substrate 1. Hydrofluoric acid is produced by the reaction between the gas containing H2O and SAM17. As shown in FIG. 2D, the target film 18 can be etched with the generated hydrofluoric acid. The product produced by etching is volatile, vaporized and exhausted. As described above, the target film 18 is, for example, an AlO film, a SiO film, a SiN film, a ZrO film, an HfO film, or the like. All of these films can be etched with hydrofluoric acid.
　フッ酸は、上記の通り、Ｈ２Ｏを含むガスと、ＳＡＭ１７との反応によって生成する。従って、ＳＡＭ１７の近傍のみにフッ酸が生成する。それゆえ、対象膜１８の第１領域Ａ１からはみ出した不要な部位はエッチングされるのに対し、対象膜１８の第１領域Ａ１に形成された必要な部位はエッチングされない。従って、対象膜１８の不要な部位を選択的に除去できる。 As described above, hydrofluoric acid is produced by the reaction of a gas containing H2O with SAM17. Therefore, hydrofluoric acid is generated only in the vicinity of SAM17. Therefore, the unnecessary portion protruding from the first region A1 of the target film 18 is etched, whereas the necessary portion formed in the first region A1 of the target film 18 is not etched. Therefore, unnecessary portions of the target film 18 can be selectively removed.
　ここで、本開示の技術と、非特許文献１の技術とを比較する。非特許文献１には、ＡｌＯ膜の表面に対してフッ酸とＴＭＡとを交互に供給し、ＡｌＯ膜の表面をエッチングする、原子層エッチング（ＡＬＥ）が記載されている。しかし、非特許文献１に記載のＡＬＥでは、ＡｌＯ膜の表面全体がエッチングされてしまい、必要な部分までエッチングされてしまう。また、非特許文献１に記載の方法では、処理温度が高く（例えば３００℃以上、好ましくは３５０℃以上）、基板１にダメージが生じる恐れがある。ダメージの具体例としては、例えば金属膜１２のフッ化又は合金化が挙げられる。合金化は、対象膜１８の原料ガス（例えばＴＭＡ）に含まれる金属と、金属膜１２との反応によって生じる。 Here, the technique of the present disclosure is compared with the technique of Non-Patent Document 1. Non-Patent Document 1 describes atomic layer etching (ALE) in which hydrofluoric acid and TMA are alternately supplied to the surface of an ALO film to etch the surface of the ALO film. However, in the ALE described in Non-Patent Document 1, the entire surface of the AlO film is etched, and even a necessary portion is etched. Further, in the method described in Non-Patent Document 1, the processing temperature is high (for example, 300 ° C. or higher, preferably 350 ° C. or higher), and the substrate 1 may be damaged. Specific examples of damage include fluorination or alloying of the metal film 12. The alloying occurs by the reaction between the metal contained in the raw material gas (for example, TMA) of the target film 18 and the metal film 12.
　本開示の技術によれば、上記の通り、対象膜１８の第１領域Ａ１からはみ出した不要な部位はエッチングされるのに対し、対象膜１８の第１領域Ａ１に形成された必要な部位はエッチングされない。従って、対象膜１８の不要な部位を選択的に除去できる。その結果、基板１の配線抵抗を低減できる。また、本実施形態のステップＳ７では、処理温度が例えば２００℃以下である。それゆえ、基板１のダメージの発生を抑制できる。 According to the technique of the present disclosure, as described above, the unnecessary portion protruding from the first region A1 of the target film 18 is etched, whereas the necessary portion formed in the first region A1 of the target film 18 is Not etched. Therefore, unnecessary portions of the target film 18 can be selectively removed. As a result, the wiring resistance of the substrate 1 can be reduced. Further, in step S7 of the present embodiment, the processing temperature is, for example, 200 ° C. or lower. Therefore, it is possible to suppress the occurrence of damage to the substrate 1.
　図１のステップＳ７は、例えば図４に示すステップＳ７１～Ｓ７３を含む。先ず、ステップＳ７１では、基板１の表面１ａに対してＨ２Ｏを含むガス（Ｈ２Ｏ含有ガス）を供給する。Ｈ２Ｏ含有ガスは、Ｈ２Ｏガスのみを含んでもよいし、Ｈ２Ｏガスとキャリアガスを含んでもよい。また、Ｈ２Ｏ含有ガスは、Ｈ２Ｏガスの他に、カルボン酸等の有機酸のガスを含んでもよい。 Step S7 in FIG. 1 includes, for example, steps S71 to S73 shown in FIG. First, in step S71, a gas containing H 2 O (a gas containing H 2 O) is supplied to the surface 1a of the substrate 1. The H 2 O-containing gas may contain only the H 2 O gas, or may contain the H 2 O gas and the carrier gas. Further, the H 2 O-containing gas may contain an organic acid gas such as a carboxylic acid in addition to the H 2 O gas.
　次に、ステップＳ７２では、基板１の表面１ａに対してプラズマ化されたガス（プラズマ化ガス）を供給する。プラズマ化ガスは、例えばＨ２ガス、Ａｒガス、Ｎ２ガス、及びＮＨ３ガスから選ばれる少なくとも１つを含む。プラズマ化ガスの供給によってＳＡＭ１７を分解でき、フッ酸の生成を促進できる。フッ酸は酸性であるので、フッ酸が中和されないように、プラズマ化ガスは還元性ガス又は不活性ガスであることが好ましい。なお、ステップＳ７１とステップＳ７２の順番は逆でもよい。 Next, in step S72, a plasmatized gas (plasmaized gas) is supplied to the surface 1a of the substrate 1. The plasmatized gas comprises at least one selected from, for example, H 2 gas, Ar gas, N 2 gas, and NH 3 gas. The supply of plasmatized gas can decompose SAM17 and promote the production of hydrofluoric acid. Since hydrofluoric acid is acidic, the plasmatized gas is preferably a reducing gas or an inert gas so that the hydrofluoric acid is not neutralized. The order of steps S71 and S72 may be reversed.
　次に、ステップＳ７３では、ステップＳ７１～Ｓ７２を設定回数実施したか否かをチェックする。実施回数が設定回数に達していない場合（ステップＳ７３、ＮＯ）、ステップＳ７１～Ｓ７２を再度実施する。一方、実施回数が設定回数に達している場合（ステップＳ７３、ＹＥＳ）、今回の処理を終了する。 Next, in step S73, it is checked whether or not steps S71 to S72 have been executed a set number of times. If the number of executions has not reached the set number of times (steps S73, NO), steps S71 to S72 are executed again. On the other hand, when the number of executions has reached the set number of times (step S73, YES), the current process is terminated.
　図４では、Ｈ２Ｏ含有ガスと、プラズマ化ガスとを順番に供給し、同時に供給しないが、同時に供給してもよい。いずれにしろ、プラズマ化ガスの供給によってＳＡＭ１７を分解でき、フッ酸の生成を促進できる。但し、Ｈ２Ｏ含有ガスとプラズマ化ガスを順番に供給すれば、Ｈ２Ｏ含有ガスのプラズマ化を防止でき、酸素プラズマの発生を防止でき、基板１の表面１ａの酸化を防止できる。 In FIG. 4, the H2O -containing gas and the plasmatized gas are supplied in order and are not supplied at the same time, but may be supplied at the same time. In any case, the supply of plasmatized gas can decompose SAM17 and promote the production of hydrofluoric acid. However, if the H 2 O-containing gas and the plasmatized gas are supplied in order, the H 2 O-containing gas can be prevented from being plasmatized, the generation of oxygen plasma can be prevented, and the oxidation of the surface 1a of the substrate 1 can be prevented.
　また、ステップＳ７３の設定回数は、１回でもよいが、複数回であることが好ましい。プラズマ化ガスの供給を複数回に分けることにより、ＳＡＭ１７の分解を徐々に進めることができ、フッ酸を長時間に亘って生成でき、不要な部位の幅Ｗを狭めることができる。その結果、基板１の配線抵抗を低減できる。ステップＳ７３の設定回数は、例えば５～５０である。 Further, the number of times of setting in step S73 may be once, but is preferably a plurality of times. By dividing the supply of the plasmatized gas into a plurality of times, the decomposition of SAM 17 can be gradually promoted, hydrofluoric acid can be generated over a long period of time, and the width W of an unnecessary portion can be narrowed. As a result, the wiring resistance of the substrate 1 can be reduced. The number of times of setting in step S73 is, for example, 5 to 50.
　ステップＳ７の処理条件の一例を下記に示す。
・ステップＳ７１
Ｈ２Ｏガスの流量：５０ｓｃｃｍ～２００ｓｃｃｍ
処理時間：１ｓｅｃ～３０ｓｅｃ
・ステップＳ７２
Ｈ２ガスの流量：２００ｓｃｃｍ～３０００ｓｃｃｍ
Ａｒガスの流量：１００ｓｃｃｍ～６０００ｓｃｃｍ
Ｈ２ガスとＡｒガスの混合ガスに占めるＨ２ガスの割合：２０体積％～９０体積％
プラズマ生成用の電源周波数：４０ＭＨｚ
プラズマ生成用の電力：１００～６００Ｗ
処理時間：１０ｓｅｃ～３０ｓｅｃ
・ステップＳ７１～Ｓ７２に共通の処理条件
処理温度：１２０℃
処理圧力：２６６Ｐａ。 An example of the processing conditions in step S7 is shown below.
-Step S71
H2 O gas flow rate: 50 sccm- 200 sccm
Processing time: 1 sec to 30 sec
-Step S72
Flow rate of H2 gas: 200 sccm-3000 sccm
Ar gas flow rate: 100 sccm-6000 sccm
Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 20% by volume to 90% by volume
Power frequency for plasma generation: 40MHz
Power for plasma generation: 100-600W
Processing time: 10 sec to 30 sec
-Processing conditions common to steps S71 to S72 Processing temperature: 120 ° C.
Processing pressure: 266 Pa.
　ステップＳ７では、図２Ｄに示すように、ほとんどのＳＡＭ１７が、分解除去されてもよい。ステップＳ７の後には、ＳＡＭ１７が、基板１の表面１ａに残らなくてもよい。 In step S7, as shown in FIG. 2D, most of the SAM 17 may be decomposed and removed. After step S7, the SAM 17 does not have to remain on the surface 1a of the substrate 1.
　なお、図示しないが、ステップＳ７は、途中で、第１領域Ａ１にＳＡＭ１７を形成し、補給することを含んでもよい。ＳＡＭ１７の補給によって、フッ酸を長時間に亘って生成でき、不要な部位の幅Ｗを狭めることができ、基板１の配線抵抗を低減できる。その場合、ＳＡＭ１７形成前にＯ２ガスあるいはＨ２Ｏガスを供給すると、より多くのＳＡＭ１７を形成できる。 Although not shown, step S7 may include forming and replenishing SAM17 in the first region A1 on the way. By replenishing the SAM 17, hydrofluoric acid can be generated over a long period of time, the width W of an unnecessary portion can be narrowed, and the wiring resistance of the substrate 1 can be reduced. In that case, if O 2 gas or H 2 O gas is supplied before the formation of SAM 17, more SAM 17 can be formed.
　次に、図１のステップＳ８では、ステップＳ３～Ｓ７を設定回数実施したか否かをチェックする。実施回数が設定回数に達していない場合（ステップＳ８、ＮＯ）、ステップＳ３～Ｓ７を再度実施する。一方、実施回数が設定回数に達している場合（ステップＳ８、ＹＥＳ）、ＡｌＯ膜の膜厚が最終目標の膜厚に達しているので、今回の処理を終了する。ステップＳ８の設定回数は、ＡｌＯ膜の最終目標の膜厚に応じて設定される。 Next, in step S8 of FIG. 1, it is checked whether or not steps S3 to S7 have been executed a set number of times. If the number of executions has not reached the set number of times (steps S8, NO), steps S3 to S7 are executed again. On the other hand, when the number of times of execution has reached the set number of times (step S8, YES), the film thickness of the AlO film has reached the final target film thickness, so the current process is terminated. The number of times of setting in step S8 is set according to the final target film thickness of the AlO film.
　ステップＳ８の設定回数は、１回でもよいが、複数回であることが好ましい。ＡｌＯ膜の形成を複数回に分けて実施すれば、１回で実施する場合に比べて、各回のステップＳ６において対象膜１８の不要な部位の幅Ｗを狭くできる。その幅Ｗが狭いほど、不要な部位の除去が容易である。従って、ＡｌＯ膜の形成を複数回に分けて実施すれば、１回で実施する場合に比べて、最終的に得られる対象膜１８の不要な部位の幅Ｗを狭くでき、基板１の配線抵抗を低減できる。 The number of times of setting in step S8 may be once, but is preferably a plurality of times. If the formation of the AlO film is carried out in a plurality of times, the width W of the unnecessary portion of the target film 18 can be narrowed in each step S6 as compared with the case where the formation of the AlO film is carried out once. The narrower the width W, the easier it is to remove unnecessary parts. Therefore, if the formation of the AlO film is carried out in a plurality of times, the width W of the unnecessary portion of the target film 18 finally obtained can be narrowed as compared with the case where the formation is carried out once, and the wiring resistance of the substrate 1 can be narrowed. Can be reduced.
　図１に示すように、ｎ（ｎは１以上の自然数）回目のステップＳ７の後であって、ｎ＋１回目のステップＳ５の前に、ステップＳ３が実施されてもよい。ステップＳ３の再実施は、ステップＳ７においてプラズマ化されたＨ２ガスを基板１の表面１ａに供給する場合に有効である。この場合、ステップＳ７において、ステップＳ２と同様に、金属膜１２の表面が還元されるからである。ステップＳ７の後にステップＳ３を実施すれば、金属膜１２の表面を適度に酸化できる。その結果、その後に実施されるステップＳ５において、金属膜１２の表面に緻密なＳＡＭ１７を形成できる。 As shown in FIG. 1, step S3 may be performed after the n (n is a natural number of 1 or more) th step S7 and before the n + 1th step S5. The re-execution of step S3 is effective when the plasmalized H2 gas in step S7 is supplied to the surface 1a of the substrate 1. In this case, in step S7, the surface of the metal film 12 is reduced as in step S2. If step S3 is carried out after step S7, the surface of the metal film 12 can be appropriately oxidized. As a result, in the subsequent step S5, a dense SAM 17 can be formed on the surface of the metal film 12.
　次に、図５Ａ～図５Ｄを参照して、第１変形例に係る基板１の処理について説明する。本変形例の基板１は、図５Ａに示すように、その表面１ａに、ライナー膜１４が露出する第４領域Ａ４を更に有する。第４領域Ａ４は、第２領域Ａ２と第３領域Ａ３の間に形成される。ライナー膜１４は、バリア膜１３の上に形成され、金属膜１２の形成を支援する。金属膜１２は、ライナー膜１４の上に形成される。ライナー膜１４は、特に限定されないが、例えば、Ｃｏ膜、又はＲｕ膜である。 Next, the processing of the substrate 1 according to the first modification will be described with reference to FIGS. 5A to 5D. As shown in FIG. 5A, the substrate 1 of this modification further has a fourth region A4 on the surface 1a on which the liner film 14 is exposed. The fourth region A4 is formed between the second region A2 and the third region A3. The liner film 14 is formed on the barrier film 13 and supports the formation of the metal film 12. The metal film 12 is formed on the liner film 14. The liner film 14 is not particularly limited, but is, for example, a Co film or a Ru film.
　表２に、絶縁膜１１と、金属膜１２と、バリア膜１３と、ライナー膜１４との具体例をまとめて示す。 Table 2 summarizes specific examples of the insulating film 11, the metal film 12, the barrier film 13, and the liner film 14.
Figure JPOXMLDOC01-appb-T000002
 　なお、絶縁膜１１と、金属膜１２と、バリア膜１３と、ライナー膜１４との組み合わせは、特に限定されない。
Figure JPOXMLDOC01-appb-T000002
 The combination of the insulating film 11, the metal film 12, the barrier film 13, and the liner film 14 is not particularly limited.
　ところで、ＳＡＭ１７の原料は、絶縁膜１１に比べてライナー膜１４にも化学吸着しやすい。 By the way, the raw material of SAM 17 is more easily chemically adsorbed to the liner film 14 than the insulating film 11.
　それゆえ、本変形例のステップＳ５では、図５Ｂに示すように、第１領域Ａ１、第２領域Ａ２、第３領域Ａ３及び第４領域Ａ４の中で、第２領域Ａ２、第３領域Ａ３及び第４領域Ａ４に選択的に、有機化合物を化学吸着し、ＳＡＭ１７を形成する。ＳＡＭ１７は、第１領域Ａ１には形成されない。 Therefore, in step S5 of this modification, as shown in FIG. 5B, in the first region A1, the second region A2, the third region A3, and the fourth region A4, the second region A2 and the third region A3 And, the organic compound is selectively chemically adsorbed to the fourth region A4 to form SAM17. SAM17 is not formed in the first region A1.
　また、本変形例のステップＳ６では、図５Ｃに示すように、ＳＡＭ１７を用い第２領域Ａ２、第３領域Ａ３及び第４領域Ａ４における対象膜１８の形成を阻害しつつ、第１領域Ａ１に対象膜１８を形成する。ＳＡＭ１７は対象膜１８の形成を阻害するが、ＳＡＭ１７のブロック性能は完全ではなく、対象膜１８は第１領域Ａ１から横にはみ出してしまう。 Further, in step S6 of this modification, as shown in FIG. 5C, SAM17 is used to inhibit the formation of the target film 18 in the second region A2, the third region A3, and the fourth region A4, and the first region A1 is formed. The target film 18 is formed. 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 first region A1.
　そこで、本変形例のステップＳ７では、図５Ｄに示すように、基板１の表面１ａに対してＨ２Ｏを含むガスを供給し、対象膜１８の第１領域Ａ１からはみ出した不要な部位をエッチングする。従って、対象膜１８の不要な部位を選択的に除去できる。 Therefore, in step S7 of this modification, as shown in FIG. 5D, a gas containing H 2 O is supplied to the surface 1a of the substrate 1, and an unnecessary portion protruding from the first region A1 of the target film 18 is removed. Etch. Therefore, unnecessary portions of the target film 18 can be selectively removed.
　次に、図６Ａ～図６Ｄを参照して、第２変形例に係る基板１の処理について説明する。本変形例の基板１は、図６Ａに示すように、金属膜１２がキャップ膜である。絶縁膜１１の凹部には、金属膜１２とは異なる金属で形成される第２金属膜１５が埋め込まれる。第２金属膜１５の上に金属膜１２が形成され、金属膜１２は第２金属膜１５を覆う。 Next, the processing of the substrate 1 according to the second modification will be described with reference to FIGS. 6A to 6D. As shown in FIG. 6A, the metal film 12 of the substrate 1 of this modification is a cap film. A second metal film 15 made of a metal different from the metal film 12 is embedded in the recess of the insulating film 11. A metal film 12 is formed on the second metal film 15, and the metal film 12 covers the second metal film 15.
　表３に、絶縁膜１１と、金属膜（キャップ膜）１２と、バリア膜１３と、ライナー膜１４と、第２金属膜１５との具体例をまとめて示す。 Table 3 summarizes specific examples of the insulating film 11, the metal film (cap film) 12, the barrier film 13, the liner film 14, and the second metal film 15.
Figure JPOXMLDOC01-appb-T000003
 　なお、絶縁膜１１と、金属膜１２と、バリア膜１３と、ライナー膜１４と、第２金属膜１５との組み合わせは、特に限定されない。
Figure JPOXMLDOC01-appb-T000003
 The combination of the insulating film 11, the metal film 12, the barrier film 13, the liner film 14, and the second metal film 15 is not particularly limited.
　本変形例のステップＳ５では、図６Ｂに示すように、第１領域Ａ１、第２領域Ａ２、第３領域Ａ３及び第４領域Ａ４の中で、第２領域Ａ２、第３領域Ａ３及び第４領域Ａ４に選択的に、有機化合物を化学吸着し、ＳＡＭ１７を形成する。ＳＡＭ１７は、第１領域Ａ１には形成されない。 In step S5 of this modification, as shown in FIG. 6B, in the first region A1, the second region A2, the third region A3, and the fourth region A4, the second region A2, the third region A3, and the fourth region A4. The organic compound is selectively chemically adsorbed on the region A4 to form SAM17. SAM17 is not formed in the first region A1.
　また、本変形例のステップＳ６では、図６Ｃに示すように、ＳＡＭ１７を用い第２領域Ａ２、第３領域Ａ３及び第４領域Ａ４における対象膜１８の形成を阻害しつつ、第１領域Ａ１に対象膜１８を形成する。ＳＡＭ１７は対象膜１８の形成を阻害するが、ＳＡＭ１７のブロック性能は完全ではなく、対象膜１８は第１領域Ａ１から横にはみ出してしまう。 Further, in step S6 of this modification, as shown in FIG. 6C, SAM17 is used to inhibit the formation of the target film 18 in the second region A2, the third region A3, and the fourth region A4, and the first region A1 is formed. The target film 18 is formed. 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 first region A1.
　そこで、本変形例のステップＳ７では、図６Ｄに示すように、基板１の表面１ａに対してＨ２Ｏを含むガスを供給し、対象膜１８の第１領域Ａ１からはみ出した不要な部位をエッチングする。従って、対象膜１８の不要な部位を選択的に除去できる。 Therefore, in step S7 of this modification, as shown in FIG. 6D, a gas containing H 2 O is supplied to the surface 1a of the substrate 1, and an unnecessary portion protruding from the first region A1 of the target film 18 is removed. Etch. Therefore, unnecessary portions of the target film 18 can be selectively removed.
　なお、上記実施形態、上記第１変形例、及び上記第２変形例では、絶縁膜１１が第１膜に相当し、金属膜１２が第２膜に相当するが、第１膜と第２膜の組み合わせは特に限定されない。 In the above-described embodiment, the above-mentioned first modification, and the above-mentioned second modification, the insulating film 11 corresponds to the first film and the metal film 12 corresponds to the second film, but the first film and the second film. The combination of is not particularly limited.
　表４に、ＳＡＭ１７の原料がチオール系化合物である場合の、第１膜と第２膜と対象膜１８の組み合わせの候補を示す。 Table 4 shows candidates for combinations of the first film, the second film, and the target film 18 when the raw material of SAM 17 is a thiol-based compound.
Figure JPOXMLDOC01-appb-T000004
 表４に記載の候補は、任意の組み合わせで用いられる。
Figure JPOXMLDOC01-appb-T000004
 The candidates shown in Table 4 are used in any combination.
　また、表５に、ＳＡＭ１７の原料がホスホン酸系化合物である場合の、第１膜と第２膜と対象膜１８の組み合わせの候補を示す。 Table 5 shows candidates for combinations of the first film, the second film, and the target film 18 when the raw material of SAM 17 is a phosphonic acid compound.
Figure JPOXMLDOC01-appb-T000005
 表５に記載の候補は、任意の組み合わせで用いられる。
Figure JPOXMLDOC01-appb-T000005
 The candidates shown in Table 5 are used in any combination.
　第１膜は絶縁膜であり、第２膜は導電膜であり、第１膜の上に形成される対象膜１８は絶縁膜であることが好ましい。 It is preferable that the first film is an insulating film, the second film is a conductive film, and the target film 18 formed on the first film is an insulating film.
　次に、図７を参照して、上記の成膜方法を実施する成膜装置１００について説明する。図７に示すように、成膜装置１００は、第１処理部２００Ａと、第２処理部２００Ｂと、第３処理部２００Ｃと、搬送部４００と、制御部５００とを有する。第１処理部２００Ａは、図１のステップＳ２～Ｓ３を実施する。第２処理部２００Ｂは、図１のステップＳ４～Ｓ５を実施する。第３処理部２００Ｃは、図１のステップＳ６～Ｓ７を実施する。第１処理部２００Ａと、第２処理部２００Ｂと、第３処理部２００Ｃとは、同様の構造を有する。従って、第１処理部２００Ａのみで、図１のステップＳ２～Ｓ７の全てを実施することも可能である。搬送部４００は、第１処理部２００Ａ、第２処理部２００Ｂ、及び第３処理部２００Ｃに対して、基板１を搬送する。制御部５００は、第１処理部２００Ａ、第２処理部２００Ｂ、第３処理部２００Ｃ、及び搬送部４００を制御する。 Next, the film forming apparatus 100 that implements the above film forming method will be described with reference to FIG. 7. As shown in FIG. 7, the film forming apparatus 100 includes a first processing unit 200A, a second processing unit 200B, a third processing unit 200C, a transport unit 400, and a control unit 500. The first processing unit 200A carries out steps S2 to S3 of FIG. The second processing unit 200B carries out steps S4 to S5 of FIG. The third processing unit 200C carries out steps S6 to S7 of FIG. The first processing unit 200A, the second processing unit 200B, and the third processing unit 200C have similar structures. Therefore, it is possible to carry out all of steps S2 to S7 in FIG. 1 only by the first processing unit 200A. The transport unit 400 transports the substrate 1 to the first processing unit 200A, the second processing unit 200B, and the third processing unit 200C. The control unit 500 controls the first processing unit 200A, the second processing unit 200B, the third processing unit 200C, and the transport unit 400.
　搬送部４００は、第１搬送室４０１と、第１搬送機構４０２とを有する。第１搬送室４０１の内部雰囲気は、大気雰囲気である。第１搬送室４０１の内部に、第１搬送機構４０２が設けられる。第１搬送機構４０２は、基板１を保持するアーム４０３を含み、レール４０４に沿って走行する。レール４０４は、キャリアＣの配列方向に延びている。 The transport unit 400 has a first transport chamber 401 and a first transport mechanism 402. The internal atmosphere of the first transport chamber 401 is an atmospheric atmosphere. A first transport mechanism 402 is provided inside the first transport chamber 401. The first transport mechanism 402 includes an arm 403 that holds the substrate 1 and travels along the rail 404. The rail 404 extends in the arrangement direction of the carriers C.
　また、搬送部４００は、第２搬送室４１１と、第２搬送機構４１２とを有する。第２搬送室４１１の内部雰囲気は、真空雰囲気である。第２搬送室４１１の内部に、第２搬送機構４１２が設けられる。第２搬送機構４１２は、基板１を保持するアーム４１３を含み、アーム４１３は、鉛直方向及び水平方向に移動可能に、且つ鉛直軸周りに回転可能に配置される。第２搬送室４１１には、異なるゲートバルブＧを介して第１処理部２００Ａと第２処理部２００Ｂと第３処理部２００Ｃとが接続される。 Further, the transport unit 400 has a second transport chamber 411 and a second transport mechanism 412. The internal atmosphere of the second transport chamber 411 is a vacuum atmosphere. A second transport mechanism 412 is provided inside the second transport chamber 411. The second transfer mechanism 412 includes an arm 413 that holds the substrate 1, and the arm 413 is arranged so as to be movable in the vertical direction and the horizontal direction and rotatably around the vertical axis. The first processing unit 200A, the second processing unit 200B, and the third processing unit 200C are connected to the second transfer chamber 411 via different gate valves G.
　更に、搬送部４００は、第１搬送室４０１と第２搬送室４１１の間に、ロードロック室４２１を有する。ロードロック室４２１の内部雰囲気は、図示しない調圧機構により真空雰囲気と大気雰囲気との間で切り換えられる。これにより、第２搬送室４１１の内部を常に真空雰囲気に維持できる。また、第１搬送室４０１から第２搬送室４１１にガスが流れ込むのを抑制できる。第１搬送室４０１とロードロック室４２１の間、及び第２搬送室４１１とロードロック室４２１の間には、ゲートバルブＧが設けられる。 Further, the transport unit 400 has a load lock chamber 421 between the first transport chamber 401 and the second transport 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). As a result, the inside of the second transport chamber 411 can always be maintained in a vacuum atmosphere. Further, it is possible to suppress the inflow of gas from the first transport chamber 401 to the second transport chamber 411. A gate valve G is provided between the first transport chamber 401 and the load lock chamber 421, and between the second transport chamber 411 and the load lock chamber 421.
　制御部５００は、例えばコンピュータであり、ＣＰＵ（Ｃｅｎｔｒａｌ　Ｐｒｏｃｅｓｓｉｎｇ　Ｕｎｉｔ）５０１と、メモリ等の記憶媒体５０２とを有する。記憶媒体５０２には、成膜装置１００において実行される各種の処理を制御するプログラムが格納される。制御部５００は、記憶媒体５０２に記憶されたプログラムをＣＰＵ５０１に実行させることにより、成膜装置１００の動作を制御する。制御部５００は、第１処理部２００Ａと第２処理部２００Ｂと第３処理部２００Ｃと搬送部４００とを制御し、上記の成膜方法を実施する。 The control unit 500 is, for example, a computer, and has a CPU (Central Processing Unit) 501 and a storage medium 502 such as a memory. The storage medium 502 stores programs that control various processes executed by the film forming apparatus 100. The control unit 500 controls the operation of the film forming apparatus 100 by causing the CPU 501 to execute the program 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, and the transport unit 400, and implements the above film forming method.
　次に、成膜装置１００の動作について説明する。先ず、第１搬送機構４０２が、キャリアＣから基板１を取り出し、取り出した基板１をロードロック室４２１に搬送し、ロードロック室４２１から退出する。次に、ロードロック室４２１の内部雰囲気が大気雰囲気から真空雰囲気に切り換えられる。その後、第２搬送機構４１２が、ロードロック室４２１から基板１を取り出し、取り出した基板１を第１処理部２００Ａに搬送する。 Next, the operation of the film forming apparatus 100 will be described. First, the first transport mechanism 402 takes out the substrate 1 from the carrier C, conveys the taken out substrate 1 to the load lock chamber 421, and exits from the load lock chamber 421. Next, the internal atmosphere of the load lock chamber 421 is switched from the atmospheric atmosphere to the vacuum atmosphere. After that, the second transfer mechanism 412 takes out the substrate 1 from the load lock chamber 421 and conveys the taken out substrate 1 to the first processing unit 200A.
　次に、第１処理部２００Ａが、ステップＳ２～Ｓ３を実施する。その後、第２搬送機構４１２が、第１処理部２００Ａから基板１を取り出し、取り出した基板１を第２処理部２００Ｂに搬送する。この間、基板１の周辺雰囲気を真空雰囲気に維持でき、基板１の酸化を抑制できる。 Next, the first processing unit 200A carries out steps S2 to S3. After that, the second transfer mechanism 412 takes out the substrate 1 from the first processing unit 200A and conveys the taken out 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.
　次に、第２処理部２００Ｂが、ステップＳ４～Ｓ５を実施する。その後、第２搬送機構４１２が、第２処理部２００Ｂから基板１を取り出し、取り出した基板１を第３処理部２００Ｃに搬送する。この間、基板１の周辺雰囲気を真空雰囲気に維持でき、ＳＡＭ１７のブロック性能の低下を抑制できる。 Next, the second processing unit 200B carries out steps S4 to S5. After that, the second transfer mechanism 412 takes out the substrate 1 from the second processing unit 200B, and conveys the taken out 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 deterioration of the block performance of the SAM 17 can be suppressed.
　次に、第３処理部２００Ｃが、ステップＳ６～Ｓ７を実施する。続いて、制御部５００は、ステップＳ３～Ｓ７を設定回数実施したか否かをチェックする。実施回数が設定回数に達していない場合、第２搬送機構４１２は、第３処理部２００Ｃから基板１を取り出し、取り出した基板１を第１処理部２００Ａに搬送する。その後、制御部５００は、第１処理部２００Ａと第２処理部２００Ｂと第３処理部２００Ｃと搬送部４００とを制御し、ステップＳ３～Ｓ７を実施する。 Next, the third processing unit 200C carries out steps S6 to S7. Subsequently, the control unit 500 checks whether or not steps S3 to S7 have been executed a set number of times. When the number of implementations has not reached the set number of times, the second transfer mechanism 412 takes out the substrate 1 from the third processing unit 200C and conveys the taken out substrate 1 to the first processing unit 200A. After that, the control unit 500 controls the first processing unit 200A, the second processing unit 200B, the third processing unit 200C, and the transport unit 400, and carries out steps S3 to S7.
　一方、実施回数が設定回数に達している場合、第２搬送機構４１２が、第３処理部２００Ｃから基板１を取り出し、取り出した基板１をロードロック室４２１に搬送し、ロードロック室４２１から退出する。続いて、ロードロック室４２１の内部雰囲気が真空雰囲気から大気雰囲気に切り換えられる。その後、第１搬送機構４０２が、ロードロック室４２１から基板１を取り出し、取り出した基板１をキャリアＣに収容する。そして、基板１の処理が終了する。 On the other hand, when the number of executions has reached the set number of times, the second transfer mechanism 412 takes out the substrate 1 from the third processing unit 200C, conveys the taken out substrate 1 to the load lock chamber 421, and exits from the load lock chamber 421. do. Subsequently, the internal atmosphere of the load lock chamber 421 is switched from the vacuum atmosphere to the atmospheric atmosphere. After that, the first transfer mechanism 402 takes out the substrate 1 from the load lock chamber 421 and accommodates the taken out substrate 1 in the carrier C. Then, the processing of the substrate 1 is completed.
　次に、図８を参照して、第１処理部２００Ａについて説明する。なお、第２処理部２００Ｂ及び第３処理部２００Ｃは、第１処理部２００Ａと同様に構成されるので、図示及び説明を省略する。 Next, the first processing unit 200A will be described with reference to FIG. Since the second processing unit 200B and the third processing unit 200C are configured in the same manner as the first processing unit 200A, illustration and description thereof will be omitted.
　第１処理部２００Ａは、略円筒状の気密な処理容器２１０を備える。処理容器２１０の底壁の中央部には、排気室２１１が設けられている。排気室２１１は、下方に向けて突出する例えば略円筒状の形状を備える。排気室２１１には、例えば排気室２１１の側面において、排気配管２１２が接続されている。 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, for example, a substantially cylindrical shape that projects downward. An exhaust pipe 212 is connected to the exhaust chamber 211, for example, on the side surface of the exhaust chamber 211.
　排気配管２１２には、圧力制御器２７１を介して排気源２７２が接続されている。圧力制御器２７１は、例えばバタフライバルブ等の圧力調整バルブを備える。排気配管２１２は、排気源２７２によって処理容器２１０内を減圧できるように構成されている。圧力制御器２７１と、排気源２７２とで、処理容器２１０内のガスを排出するガス排出機構２７０が構成される。 The exhaust source 272 is connected to the exhaust pipe 212 via the pressure controller 271. The pressure controller 271 includes a pressure adjusting valve such as a butterfly valve. The exhaust pipe 212 is configured so that the inside of the processing container 210 can be depressurized by the exhaust source 272. The pressure controller 271 and the exhaust source 272 form a gas discharge mechanism 270 that discharges the gas in the processing container 210.
　処理容器２１０の側面には、搬送口２１５が設けられている。搬送口２１５は、ゲートバルブＧによって開閉される。処理容器２１０内と第２搬送室４１１（図７参照）との間における基板１の搬入出は、搬送口２１５を介して行われる。 A transport port 215 is provided on the side surface of the processing container 210. The transport port 215 is opened and closed by the gate valve G. The loading and unloading of the substrate 1 between the inside of the processing container 210 and the second transport chamber 411 (see FIG. 7) is performed via the transport port 215.
　処理容器２１０内には、基板１を保持する保持部であるステージ２２０が設けられている。ステージ２２０は、基板１の表面１ａを上に向けて、基板１を水平に保持する。ステージ２２０は、平面視で略円形状に形成されており、支持部材２２１によって支持されている。ステージ２２０の表面には、例えば直径が３００ｍｍの基板１を載置するための略円形状の凹部２２２が形成されている。凹部２２２は、基板１の直径よりも僅かに大きい内径を有する。凹部２２２の深さは、例えば基板１の厚さと略同一に構成される。ステージ２２０は、例えば窒化アルミニウム（ＡｌＮ）等のセラミックス材料により形成されている。また、ステージ２２０は、ニッケル（Ｎｉ）等の金属材料により形成されていてもよい。なお、凹部２２２の代わりにステージ２２０の表面の周縁部に基板１をガイドするガイドリングを設けてもよい。 A stage 220, which is a holding portion for holding the substrate 1, is provided in the processing container 210. The stage 220 holds the substrate 1 horizontally with the surface 1a of the substrate 1 facing up. The stage 220 is formed in a substantially circular shape in a plan view, and is supported by the support member 221. On the surface of the stage 220, for example, a substantially circular recess 222 for mounting the substrate 1 having a diameter of 300 mm is formed. The recess 222 has an inner diameter slightly larger than the diameter of the substrate 1. The depth of the recess 222 is configured to be substantially the same as, for example, the thickness of the substrate 1. The stage 220 is made of a ceramic material such as aluminum nitride (AlN). Further, the stage 220 may be formed of a metal 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.
　ステージ２２０には、例えば接地された下部電極２２３が埋設される。下部電極２２３の下方には、加熱機構２２４が埋設される。加熱機構２２４は、制御部５００（図７参照）からの制御信号に基づいて電源部（図示せず）から給電されることによって、ステージ２２０に載置された基板１を設定温度に加熱する。ステージ２２０の全体が金属によって構成されている場合には、ステージ２２０の全体が下部電極として機能するので、下部電極２２３をステージ２２０に埋設しなくてよい。ステージ２２０には、ステージ２２０に載置された基板１を保持して昇降するための複数本（例えば３本）の昇降ピン２３１が設けられている。昇降ピン２３１の材料は、例えばアルミナ（Ａｌ２Ｏ３）等のセラミックスや石英等であってよい。昇降ピン２３１の下端は、支持板２３２に取り付けられている。支持板２３２は、昇降軸２３３を介して処理容器２１０の外部に設けられた昇降機構２３４に接続されている。 For example, a grounded lower electrode 223 is embedded in the stage 220. A heating mechanism 224 is embedded below the lower electrode 223. The heating mechanism 224 heats the substrate 1 mounted on the stage 220 to a set temperature by supplying power from a power supply unit (not shown) based on a control signal from the control unit 500 (see FIG. 7). When the entire stage 220 is made of metal, the entire stage 220 functions as a lower electrode, so that the lower electrode 223 does not have to be embedded in the stage 220. The stage 220 is provided with a plurality of (for example, three) elevating pins 231 for holding and elevating the substrate 1 mounted on the stage 220. The material of the elevating pin 231 may be, for example, ceramics such as alumina (Al 2 O 3 ), quartz, or the like. The lower end of the elevating pin 231 is attached to the support plate 232. The support plate 232 is connected to an elevating mechanism 234 provided outside the processing container 210 via an elevating shaft 233.
　昇降機構２３４は、例えば排気室２１１の下部に設置されている。ベローズ２３５は、排気室２１１の下面に形成された昇降軸２３３用の開口部２１９と昇降機構２３４との間に設けられている。支持板２３２の形状は、ステージ２２０の支持部材２２１と干渉せずに昇降できる形状であってもよい。昇降ピン２３１は、昇降機構２３４によって、ステージ２２０の表面の上方と、ステージ２２０の表面の下方との間で、昇降自在に構成される。 The elevating mechanism 234 is installed at the lower part of the exhaust chamber 211, for example. The bellows 235 is provided between the opening 219 for the elevating shaft 233 formed on the lower surface of the exhaust chamber 211 and the elevating mechanism 234. The shape of the support plate 232 may be a shape that can be raised and lowered without interfering with the support member 221 of the stage 220. The elevating pin 231 is vertically configured by the elevating mechanism 234 between above the surface of the stage 220 and below the surface of the stage 220.
　処理容器２１０の天壁２１７には、絶縁部材２１８を介してガス供給部２４０が設けられている。ガス供給部２４０は、上部電極を成しており、下部電極２２３に対向している。ガス供給部２４０には、整合器２５１を介して高周波電源２５２が接続されている。高周波電源２５２から上部電極（ガス供給部２４０）に４５０ｋＨｚ～１００ＭＨｚの高周波電力を供給することによって、上部電極（ガス供給部２４０）と下部電極２２３との間に高周波電界が生成され、容量結合プラズマが生成する。プラズマを生成するプラズマ生成部２５０は、整合器２５１と、高周波電源２５２と、を含む。なお、プラズマ生成部２５０は、容量結合プラズマに限らず、誘導結合プラズマなど他のプラズマを生成するものであってもよい。 The top wall 217 of the processing container 210 is provided with a gas supply unit 240 via an insulating member 218. The gas supply unit 240 forms an 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 450 kHz to 100 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 capacitively coupled plasma is generated. Is generated. The plasma generation unit 250 that generates plasma includes a matching unit 251 and a high frequency power supply 252. The plasma generation unit 250 is not limited to capacitively coupled plasma, and may generate other plasma such as inductively coupled plasma.
　ガス供給部２４０は、中空状のガス供給室２４１を備える。ガス供給室２４１の下面には、処理容器２１０内へ処理ガスを分散供給するための多数の孔２４２が例えば均等に配置されている。ガス供給部２４０における例えばガス供給室２４１の上方には、加熱機構２４３が埋設されている。加熱機構２４３は、制御部５００からの制御信号に基づいて電源部（図示せず）から給電されることによって、設定温度に加熱される。 The gas supply unit 240 includes a hollow gas supply chamber 241. On the lower surface of the gas supply chamber 241, for example, a large number of holes 242 for dispersing and supplying the processing gas into the processing container 210 are evenly arranged. A heating mechanism 243 is embedded above, for example, the gas supply chamber 241 in the gas supply unit 240. The heating mechanism 243 is heated to a set temperature by supplying power from a power supply unit (not shown) based on a control signal from the control unit 500.
　ガス供給室２４１には、ガス供給路２６１を介して、ガス供給機構２６０が接続される。ガス供給機構２６０は、ガス供給路２６１を介してガス供給室２４１に、図１のステップＳ２～Ｓ７の少なくとも１つで用いられるガスを供給する。ガス供給機構２６０は、図示しないが、ガスの種類毎に、個別配管と、個別配管の途中に設けられる開閉バルブと、個別配管の途中に設けられる流量制御器とを含む。開閉バルブが個別配管を開くと、供給源からガス供給路２６１にガスが供給される。その供給量は流量制御器によって制御される。一方、開閉バルブが個別配管を閉じると、供給源からガス供給路２６１へのガスの供給が停止される。 A gas supply mechanism 260 is connected to the gas supply chamber 241 via a gas supply path 261. The gas supply mechanism 260 supplies the gas used in at least one of steps S2 to S7 of FIG. 1 to the gas supply chamber 241 via the gas supply path 261. Although not shown, the gas supply mechanism 260 includes individual pipes, an on-off valve provided in the middle of the individual pipes, and a flow rate controller provided in the middle of the individual pipes for each type of gas, although not shown. When the on-off valve opens the individual pipe, gas is supplied from the supply source to the gas supply path 261. The supply amount is controlled by the flow rate controller. On the other hand, when the on-off valve closes the individual pipe, the supply of gas from the supply source to the gas supply path 261 is stopped.
　［実施例］
　次に、実施例について説明する。 [Example]
Next, an embodiment will be described.
　＜実施例１＞
　実施例１では、図２Ａに示す基板１を準備した。下地基板１０はシリコンウェハであり、絶縁膜１１はＳｉＯＣ膜であり、金属膜１２はＣｕ膜であり、バリア膜１３はＴａＮ膜であった。ＳｉＯＣ膜の表面において、トレンチの幅は２０ｎｍであり、トレンチのピッチは４０ｎｍであった。図１に示す成膜方法を下記の条件で実施した。ＳＡＭ１７の原料はＰＦＯＴであり、対象膜１８は膜厚５．６ｎｍのＡｌＯ膜であった。図１のステップＳ８の設定回数は１回であり、ステップＳ３～Ｓ７は１回のみ実施した。 <Example 1>
In Example 1, the substrate 1 shown in FIG. 2A was prepared. The base substrate 10 was a silicon wafer, the insulating film 11 was a SiOC film, the metal film 12 was a Cu film, and the barrier film 13 was a TaN film. On the surface of the SiOC film, the width of the trench was 20 nm and the pitch of the trench was 40 nm. The film forming method shown in FIG. 1 was carried out under the following conditions. The raw material of SAM 17 was PFOT, and the target film 18 was an AlO film having a film thickness of 5.6 nm. Step S8 in FIG. 1 was set once, and steps S3 to S7 were performed only once.
　ステップＳ２の処理条件は下記の通りであった。
Ｈ２ガスの流量：１０００ｓｃｃｍ
Ａｒガスの流量：７５０ｓｃｃｍ
Ｈ２ガスとＡｒガスの混合ガスに占めるＨ２ガスの割合：５７体積％
プラズマ生成用の電源周波数：４０ＭＨｚ
プラズマ生成用の電力：２００Ｗ
処理時間：３０ｓｅｃ
処理温度：１２０℃
処理圧力：２６６Ｐａ。 The processing conditions in step S2 were as follows.
H2 gas flow rate: 1000 sccm
Ar gas flow rate: 750 sccm
Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 57% by volume
Power frequency for plasma generation: 40MHz
Power for plasma generation: 200W
Processing time: 30 sec
Processing temperature: 120 ° C
Processing pressure: 266 Pa.
　ステップＳ３の処理条件は下記の通りであった。
Ｏ２ガスの流量：１０００ｓｃｃｍ
処理時間：９００ｓｅｃ
処理温度：１２０℃
処理圧力：２６６Ｐａ。 The processing conditions in step S3 were as follows.
O 2 gas flow rate: 1000 sccm
Processing time: 900 sec
Processing temperature: 120 ° C
Processing pressure: 266 Pa.
　ステップＳ４の処理条件は下記の通りであった。
ＩＰＡガスの流量：１００ｓｃｃｍ
処理時間：９００ｓｅｃ
処理温度：１５０℃
処理圧力：３６０Ｐａ。 The processing conditions in step S4 were as follows.
IPA gas flow rate: 100 sccm
Processing time: 900 sec
Processing temperature: 150 ° C
Processing pressure: 360 Pa.
　ステップＳ５の処理条件は下記の通りであった。
ＰＦＯＴガスの流量：１００ｓｃｃｍ
処理時間：６００ｓｅｃ
処理温度：１５０℃
処理圧力：６２０Ｐａ。 The processing conditions in step S5 were as follows.
PFOT gas flow rate: 100 sccm
Processing time: 600 sec
Processing temperature: 150 ° C
Processing pressure: 620 Pa.
　ステップＳ６の処理条件は下記の通りであった。
・ステップＳ６１
ＴＭＡガスの流量：５０ｓｃｃｍ
処理時間：０．１ｓｅｃ
・ステップＳ６２
Ａｒガスの流量：６０００ｓｃｃｍ
処理時間：１ｓｅｃ
・ステップＳ６３
Ｈ２Ｏガスの流量：１００ｓｃｃｍ
処理時間：１ｓｅｃ
・ステップＳ６４
Ａｒガスの流量：６０００ｓｃｃｍ
処理時間：２ｓｅｃ
・ステップＳ６１～Ｓ６４に共通の処理条件
処理温度：１２０℃
処理圧力：４００Ｐａ
図３のステップＳ６５の設定回数は６８回であり、ステップＳ６１～Ｓ６４は６８回繰り返し実施した。 The processing conditions in step S6 were as follows.
-Step S61
TMA gas flow rate: 50 sccm
Processing time: 0.1 sec
-Step S62
Ar gas flow rate: 6000 sccm
Processing time: 1 sec
-Step S63
H2 O gas flow rate: 100 sccm
Processing time: 1 sec
-Step S64
Ar gas flow rate: 6000 sccm
Processing time: 2 sec
-Processing conditions common to steps S61 to S64 Processing temperature: 120 ° C.
Processing pressure: 400Pa
The number of times of setting step S65 in FIG. 3 was 68 times, and steps S61 to S64 were repeated 68 times.
　ステップＳ７の処理条件は、下記の通りであった。
・ステップＳ７１
Ｈ２Ｏガスの流量：１００ｓｃｃｍ
処理時間：２ｓｅｃ
・ステップＳ７２
Ｈ２ガスの流量：２０００ｓｃｃｍ
Ａｒガスの流量：３０００ｓｃｃｍ
Ｈ２ガスとＡｒガスの混合ガスに占めるＨ２ガスの割合：４０体積％
プラズマ生成用の電源周波数：４０ＭＨｚ
プラズマ生成用の電力：２００Ｗ
処理時間：１０ｓｅｃ
・ステップＳ７１～Ｓ７２に共通の処理条件
処理温度：１２０℃
処理圧力：２６６Ｐａ
図４のステップＳ７３の設定回数は３０回であり、ステップＳ７１～Ｓ７２は３０回繰り返し実施した。 The processing conditions in step S7 were as follows.
-Step S71
H2 O gas flow rate: 100 sccm
Processing time: 2 sec
-Step S72
H 2 gas flow rate: 2000 sccm
Ar gas flow rate: 3000 sccm
Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 40% by volume
Power frequency for plasma generation: 40MHz
Power for plasma generation: 200W
Processing time: 10 sec
-Processing conditions common to steps S71 to S72 Processing temperature: 120 ° C.
Processing pressure: 266Pa
The number of times of setting step S73 in FIG. 4 was 30 times, and steps S71 to S72 were repeated 30 times.
　ステップＳ６の後であってステップＳ７の前に、対象膜１８であるＡｌＯ膜の膜厚は５．６ｎｍであり、不要な部位の幅Ｗ（図２Ｃ参照）は６．２ｎｍであった。膜厚及び幅Ｗは、基板断面のＳＥＭ写真を用いて測定した。一方、ステップＳ７の後に、不要な部位の幅Ｗは４．７ｎｍであった。従って、ステップＳ７によって、不要な部位の幅Ｗを１．５ｎｍ狭められたことが分かった。 After step S6 and before step S7, the film thickness of the AlO film, which is the target film 18, was 5.6 nm, and the width W of the unnecessary portion (see FIG. 2C) was 6.2 nm. The film thickness and width W were measured using an SEM photograph of the cross section of the substrate. On the other hand, after step S7, the width W of the unnecessary portion was 4.7 nm. Therefore, it was found that the width W of the unnecessary portion was narrowed by 1.5 nm by step S7.
　＜実施例２＞
　実施例２では、実施例１と同じ基板１を準備し、図１に示す成膜方法を下記の条件で実施した。実施例２と実施例１の主な相違点は、（１）図１のステップＳ８の設定回数を２回に設定したこと、（２）図３のステップＳ６５の設定回数を４５回に設定したこと、（３）図４のステップＳ７３の設定回数を１０回に設定したことである。なお、実施例２では、ステップＳ４は実施しなかった。 <Example 2>
In Example 2, the same substrate 1 as in Example 1 was prepared, and the film forming method shown in FIG. 1 was carried out under the following conditions. The main differences between Example 2 and Example 1 are (1) the number of times step S8 in FIG. 1 is set to 2 times, and (2) the number of times step S65 in FIG. 3 is set to 45 times. That is, (3) the number of times of setting in step S73 in FIG. 4 is set to 10 times. In Example 2, step S4 was not performed.
　ステップＳ２の処理条件は下記の通りであった。
Ｈ２ガスの流量：２０００ｓｃｃｍ
Ａｒガスの流量：３０００ｓｃｃｍ
Ｈ２ガスとＡｒガスの混合ガスに占めるＨ２ガスの割合：４０体積％
プラズマ生成用の電源周波数：４０ＭＨｚ
プラズマ生成用の電力：２００Ｗ
処理時間：１０ｓｅｃ
処理温度：１２０℃
処理圧力：２６６Ｐａ。 The processing conditions in step S2 were as follows.
H 2 gas flow rate: 2000 sccm
Ar gas flow rate: 3000 sccm
Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 40% by volume
Power frequency for plasma generation: 40MHz
Power for plasma generation: 200W
Processing time: 10 sec
Processing temperature: 120 ° C
Processing pressure: 266 Pa.
　ステップＳ３の処理条件は下記の通りであった。
Ｏ２ガスの流量：１０００ｓｃｃｍ
処理時間：６００ｓｅｃ
処理温度：１２０℃
処理圧力：２６６Ｐａ。 The processing conditions in step S3 were as follows.
O 2 gas flow rate: 1000 sccm
Processing time: 600 sec
Processing temperature: 120 ° C
Processing pressure: 266 Pa.
　ステップＳ５の処理条件は下記の通りであった。
ＰＦＯＴガスの流量：１００ｓｃｃｍ
処理時間：３００ｓｅｃ
処理温度：１５０℃
処理圧力：６２０Ｐａ。 The processing conditions in step S5 were as follows.
PFOT gas flow rate: 100 sccm
Processing time: 300 sec
Processing temperature: 150 ° C
Processing pressure: 620 Pa.
　ステップＳ６の処理条件は下記の通りであった。
・ステップＳ６１
ＴＭＡガスの流量：５０ｓｃｃｍ
処理時間：０．１ｓｅｃ
・ステップＳ６２
Ａｒガスの流量：６０００ｓｃｃｍ
処理時間：１ｓｅｃ
・ステップＳ６３
Ｈ２Ｏガスの流量：１００ｓｃｃｍ
処理時間：１ｓｅｃ
・ステップＳ６４
Ａｒガスの流量：６０００ｓｃｃｍ
処理時間：２ｓｅｃ
・ステップＳ６１～Ｓ６４に共通の処理条件
処理温度：１２０℃
処理圧力：４００Ｐａ
図３のステップＳ６５の設定回数は４５回であり、ステップＳ６１～Ｓ６４は４５回繰り返し実施した。 The processing conditions in step S6 were as follows.
-Step S61
TMA gas flow rate: 50 sccm
Processing time: 0.1 sec
-Step S62
Ar gas flow rate: 6000 sccm
Processing time: 1 sec
-Step S63
H2 O gas flow rate: 100 sccm
Processing time: 1 sec
-Step S64
Ar gas flow rate: 6000 sccm
Processing time: 2 sec
-Processing conditions common to steps S61 to S64 Processing temperature: 120 ° C.
Processing pressure: 400Pa
The number of times of setting step S65 in FIG. 3 was 45 times, and steps S61 to S64 were repeated 45 times.
　ステップＳ７の処理条件は、下記の通りであった。
・ステップＳ７１
Ｈ２Ｏガスの流量：１００ｓｃｃｍ
処理時間：２ｓｅｃ
・ステップＳ７２
Ｈ２ガスの流量：２０００ｓｃｃｍ
Ａｒガスの流量：３０００ｓｃｃｍ
Ｈ２ガスとＡｒガスの混合ガスに占めるＨ２ガスの割合：４０体積％
プラズマ生成用の電源周波数：４０ＭＨｚ
プラズマ生成用の電力：２００Ｗ
処理時間：２０ｓｅｃ
・ステップＳ７１～Ｓ７２に共通の処理条件
処理温度：１２０℃
処理圧力：２６６Ｐａ
図４のステップＳ７３の設定回数は１０回であり、ステップＳ７１～Ｓ７２は１０回繰り返し実施した。 The processing conditions in step S7 were as follows.
-Step S71
H2 O gas flow rate: 100 sccm
Processing time: 2 sec
-Step S72
H 2 gas flow rate: 2000 sccm
Ar gas flow rate: 3000 sccm
Ratio of H 2 gas to the mixed gas of H 2 gas and Ar gas: 40% by volume
Power frequency for plasma generation: 40MHz
Power for plasma generation: 200W
Processing time: 20 sec
-Processing conditions common to steps S71 to S72 Processing temperature: 120 ° C.
Processing pressure: 266Pa
The number of times of setting step S73 in FIG. 4 was 10, and steps S71 to S72 were repeated 10 times.
　実施例２と実施例１の主な相違点は、上記の通り、（１）図１のステップＳ８の設定回数を２回に設定したこと、（２）図３のステップＳ６５の設定回数を４５回に設定したこと、（３）図４のステップＳ７３の設定回数を１０回に設定したことである。 As described above, the main differences between the second embodiment and the first embodiment are that (1) the number of times the step S8 in FIG. 1 is set is set to two, and (2) the number of times the step S65 in FIG. 3 is set is 45. It was set to 10 times, and (3) the number of times of setting in step S73 in FIG. 4 was set to 10 times.
　実施例２では、全ての処理の終了後に、対象膜１８であるＡｌＯ膜の膜厚は６．０ｎｍであり、不要な部位の幅Ｗは１．０ｎｍであった。 In Example 2, after the completion of all the treatments, the film thickness of the AlO film, which is the target film 18, was 6.0 nm, and the width W of the unnecessary portion was 1.0 nm.
　実施例２と実施例１から、ＡｌＯ膜の最終目標の膜厚が同程度である場合、図１のステップＳ８の設定回数を複数回に設定し、ＡｌＯ膜の形成を複数回に分けて実施すれば、１回で実施する場合に比べて、不要な部位の幅Ｗを狭くできることが分かる。 From Example 2 and Example 1, when the final target film thickness of the AlO film is about the same, the set number of steps S8 in FIG. 1 is set to a plurality of times, and the formation of the AlO film is carried out in a plurality of times. Then, it can be seen that the width W of the unnecessary portion can be narrowed as compared with the case where the implementation is performed once.
　＜実施例３＞
　実施例３では、図４のステップＳ７２の処理時間を３０ｓｅｃに設定したこと、及び図４のステップＳ７３の設定回数を３回に設定したことを除き、実施例２と同様に、図１に示す成膜方法を実施した。 <Example 3>
In Example 3, the same as in Example 2, except that the processing time of step S72 in FIG. 4 is set to 30 sec and the number of times of setting step S73 in FIG. 4 is set to 3, it is shown in FIG. The film forming method was carried out.
　実施例３では、全ての処理の終了後に、対象膜１８であるＡｌＯ膜の膜厚は６．０ｎｍであり、不要な部位の幅Ｗは０．９ｎｍであった。従って、実施例３では、実施例２と同様の結果が得られた。 In Example 3, after the completion of all the treatments, the film thickness of the AlO film, which is the target film 18, was 6.0 nm, and the width W of the unnecessary portion was 0.9 nm. Therefore, in Example 3, the same result as in Example 2 was obtained.
　＜実施例４＞
　実施例４では、図１のステップＳ３の処理時間を３００ｓｅｃに設定したことを除き、実施例２と同様に、図１に示す成膜方法を実施した。なお、実施例２では、上記の通り、図１のステップＳ３の処理時間は６００ｓｅｃであった。 <Example 4>
In Example 4, the film forming method shown in FIG. 1 was carried out in the same manner as in Example 2, except that the processing time of step S3 in FIG. 1 was set to 300 sec. In Example 2, as described above, the processing time of step S3 in FIG. 1 was 600 sec.
　実施例４では、全ての処理の終了後に、対象膜１８であるＡｌＯ膜の膜厚は６．２ｎｍであり、不要な部位の幅Ｗは３．９ｎｍであった。なお、実施例２では、上記の通り、全ての処理の終了後に、対象膜１８であるＡｌＯ膜の膜厚は６．０ｎｍであり、不要な部位の幅Ｗは１．０ｎｍであった。 In Example 4, after the completion of all the treatments, the film thickness of the AlO film, which is the target film 18, was 6.2 nm, and the width W of the unnecessary portion was 3.9 nm. In Example 2, as described above, after the completion of all the treatments, the film thickness of the AlO film, which is the target film 18, was 6.0 nm, and the width W of the unnecessary portion was 1.0 nm.
　実施例４と実施例２とから、ステップＳ３の処理時間を３００ｓｅｃから６００ｓｅｃに延長すれば、全ての処理の終了後に、不要な部位の幅Ｗが狭くなることが分かる。ステップＳ３の処理時間がある程度長く、Ｃｕ膜の表面がある程度酸化された方が、緻密なＳＡＭが得られ、ステップＳ７において長時間亘ってフッ酸が生成されるためと推定される。 From Example 4 and Example 2, it can be seen that if the processing time of step S3 is extended from 300 sec to 600 sec, the width W of the unnecessary portion becomes narrower after the completion of all the processing. It is presumed that if the treatment time in step S3 is long to some extent and the surface of the Cu film is oxidized to some extent, a dense SAM can be obtained and hydrofluoric acid is produced over a long period of time in step S7.
　＜実施例５＞
　実施例５では、ＳｉＯＣ膜の表面におけるトレンチの幅を５０ｎｍに変更し、且つトレンチのピッチを１００ｎｍに変更したことを除き、実施例２と同じ条件で基板１の処理を実施した。 <Example 5>
In Example 5, the substrate 1 was treated under the same conditions as in Example 2 except that the width of the trench on the surface of the SiOC film was changed to 50 nm and the pitch of the trench was changed to 100 nm.
　実施例５では、全ての処理の終了後に、対象膜１８であるＡｌＯ膜の膜厚は６．４ｎｍであり、不要な部位の幅Ｗは０．０ｎｍであった。実施例５で得られた基板の断面のＳＥＭ写真を図９に示す。図９から明らかなように、ＡｌＯ膜のはみ出しは認められなかった。 In Example 5, after the completion of all the treatments, the film thickness of the AlO film, which is the target film 18, was 6.4 nm, and the width W of the unnecessary portion was 0.0 nm. FIG. 9 shows an SEM photograph of a cross section of the substrate obtained in Example 5. As is clear from FIG. 9, no protrusion of the AlO film was observed.
　以上、本開示に係る成膜方法及び成膜装置の実施形態について説明したが、本開示は上記実施形態などに限定されない。特許請求の範囲に記載された範疇内において、各種の変更、修正、置換、付加、削除、及び組み合わせが可能である。それらについても当然に本開示の技術的範囲に属する。 Although the film forming method and the embodiment of the film forming apparatus according to the present disclosure have been described above, the present disclosure is not limited to the above-described embodiment and the like. Various changes, modifications, replacements, additions, deletions, and combinations are possible within the scope of the claims. Of course, they also belong to the technical scope of the present disclosure.
　本出願は、２０２０年９月２９日に日本国特許庁に出願した特願２０２０－１６２９０２号に基づく優先権を主張するものであり、特願２０２０－１６２９０２号の全内容を本出願に援用する。 This application claims priority based on Japanese Patent Application No. 2020-16202 filed with the Japan Patent Office on September 29, 2020, and the entire contents of Japanese Patent Application No. 2020-162902 are incorporated into this application. ..
１　　基板
１ａ　表面
１１　絶縁膜（第１膜）
１２　金属膜（第２膜）
１７　ＳＡＭ（自己組織化単分子膜）
１８　対象膜
Ａ１　第１領域
Ａ２　第２領域 1 Substrate 1a Surface 11 Insulation film (first film)
12 Metal film (second film)
17 SAM (Self-assembled monolayer)
18 Target film A1 1st region A2 2nd region

Claims (10)

  1. 　第１膜が露出する第１領域と、前記第１膜とは異なる材料で形成される第２膜が露出する第２領域とを表面に有する基板を準備することと、
    　前記基板の前記表面に対して自己組織化単分子膜の原料であるフッ素を含む有機化合物を供給し、前記第１領域及び前記第２領域の中で、前記第２領域に選択的に、前記自己組織化単分子膜を形成することと、
    　前記自己組織化単分子膜を用い前記第２領域における対象膜の形成を阻害ししつつ、前記第１領域に前記対象膜を形成することと、
    　前記基板の前記表面に対してＨ２Ｏを含むガスを供給し、前記対象膜の前記第１領域からはみ出した端部をエッチングすることと、
    　を含む、成膜方法。     To prepare a substrate having a first region on which the first film is exposed and a second region on which the second film is exposed, which is made of a material different from the first film, is prepared.
    An organic compound containing fluorine, which is a raw material for a self-assembled monolayer, is supplied to the surface of the substrate, and the second region is selectively selected in the first region and the second region. Forming a self-assembled monolayer and
    Using the self-assembled monolayer to form the target film in the first region while inhibiting the formation of the target membrane in the second region.
    A gas containing H2O is supplied to the surface of the substrate to etch the end portion of the target film protruding from the first region.
    A film forming method including.
  2. 　前記対象膜の前記端部をエッチングすることは、Ｈ２Ｏを含むガスと、プラズマ化されたガスとを、前記基板の前記表面に対して供給することを含む、請求項１に記載の成膜方法。 The achievement according to claim 1, wherein etching the end portion of the target film comprises supplying a gas containing H2O and a plasmatized gas to the surface of the substrate. Membrane method.
  3. 　前記対象膜の前記端部をエッチングすることは、Ｈ２Ｏを含むガスと、プラズマ化されたガスとを、順番に、前記基板の前記表面に対して供給することを含む、請求項２に記載の成膜方法。 The second aspect of the present invention includes etching the end portion of the target film by sequentially supplying a gas containing H2O and a plasmatized gas to the surface of the substrate. The film forming method described.
  4. 　前記対象膜の前記端部をエッチングすることは、Ｈ２Ｏを含むガスと、プラズマ化されたガスとを、順番に、前記基板の前記表面に対して供給することを、複数回繰り返し含む、請求項３に記載の成膜方法。 Etching the end portion of the target film comprises repeatedly supplying the gas containing H2O and the plasmatized gas to the surface of the substrate a plurality of times. The film forming method according to claim 3.
  5. 　前記プラズマ化されたガスは、Ｈ２ガス、Ａｒガス、Ｎ２ガス、及びＮＨ３ガスから選ばれる少なくとも１つを含む、請求項２～４のいずれか１項に記載の成膜方法。 The film forming method according to any one of claims 2 to 4, wherein the plasmatized gas contains at least one selected from H 2 gas, Ar gas, N 2 gas, and NH 3 gas.
  6. 　前記対象膜の前記端部をエッチングすることは、途中で、前記第２領域に前記自己組織化単分子膜を形成し、補給することを含む、請求項１～５のいずれか１項に記載の成膜方法。 The invention according to any one of claims 1 to 5, wherein etching the end portion of the target film includes forming and replenishing the self-assembled monolayer in the second region on the way. Film formation method.
  7. 　前記自己組織化単分子膜を形成することと、前記対象膜を形成することと、前記対象膜の前記端部をエッチングすることとをこの順番で複数回繰り返し含む、請求項１～６のいずれか１項に記載に成膜方法。 Any of claims 1 to 6, wherein forming the self-assembled monolayer, forming the target film, and etching the end portion of the target film are repeated a plurality of times in this order. The film forming method described in item 1.
  8. 　ｎ（ｎは１以上の自然数）回目の前記対象膜の前記端部をエッチングすることの後であって、ｎ＋１回目の前記自己組織化単分子膜を形成することの前に、酸素を含むガスを前記基板の前記表面に対して供給することを含む、請求項７に記載に成膜方法。 A gas containing oxygen after the n (n is a natural number of 1 or more) times of etching the end of the target film and before the n + 1th time of forming the self-assembled monolayer. The film forming method according to claim 7, wherein the film is supplied to the surface of the substrate.
  9. 　前記第１膜は、絶縁膜であり、
    　前記第２膜は、導電膜であり、
    　前記第１膜の上に形成される前記対象膜は、絶縁膜である、請求項１～８のいずれか１項に記載の成膜方法。     The first film is an insulating film and is an insulating film.
    The second film is a conductive film and is
    The film forming method according to any one of claims 1 to 8, wherein the target film formed on the first film is an insulating film.
  10. 　処理容器と、
    　前記処理容器の内部で前記基板を保持する保持部と、
    　前記処理容器の内部にガスを供給するガス供給機構と、
    　前記処理容器の内部からガスを排出するガス排出機構と、
    　前記処理容器に対して前記基板を搬入出する搬送機構と、
    　前記ガス供給機構、前記ガス排出機構及び前記搬送機構を制御し、請求項１～９のいずれか１項に記載の成膜方法を実施する制御部と、
    　を備える、成膜装置。     With the processing container
    A holding portion that holds the substrate inside the processing container,
    A gas supply mechanism that supplies gas to the inside of the processing container,
    A gas discharge mechanism that discharges gas from the inside of the processing container,
    A transport mechanism for loading and unloading the substrate to and from the processing container,
    A control unit that controls the gas supply mechanism, the gas discharge mechanism, and the transport mechanism to carry out the film forming method according to any one of claims 1 to 9.
    A film forming apparatus.
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JP2018046279A (en) * 2016-09-13 2018-03-22 東京エレクトロン株式会社 Selective metal oxide deposition using self-assembled monolayer surface pretreatment
JP2020147788A (en) * 2019-03-13 2020-09-17 東京エレクトロン株式会社 Film deposition method
WO2020189288A1 (en) * 2019-03-15 2020-09-24 東京エレクトロン株式会社 Film formation method and film formation apparatus

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018046279A (en) * 2016-09-13 2018-03-22 東京エレクトロン株式会社 Selective metal oxide deposition using self-assembled monolayer surface pretreatment
JP2020147788A (en) * 2019-03-13 2020-09-17 東京エレクトロン株式会社 Film deposition method
WO2020189288A1 (en) * 2019-03-15 2020-09-24 東京エレクトロン株式会社 Film formation method and film formation apparatus

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