Substrate processing method

Abstract

A substrate processing method according to one aspect of the present disclosure comprises: a step for preparing a substrate having a resist film in which a first opening is formed; a step for supplying a first raw material containing a first metal-containing precursor, filling the first opening with a first fluid film containing a metal contained in the first metal-containing precursor at a temperature lower than the boiling point of the first metal-containing precursor, and then curing the first fluid film to form a first metal-containing film in the first opening; a step for removing the resist film to form a second opening adjacent to the first metal-containing film; a step for supplying a first film formation gas to form a first film on a side surface of the first metal-containing film; and a step for removing the first metal-containing film to form a third opening adjacent to the first film.

Description

Substrate processing method

[0001] This disclosure relates to a substrate processing method.

[0002] Patent Document 1 discloses a technique in which a side wall structure adjacent to the mandrel is removed to expose a first portion of the hard mask layer, the first portion is etched to expose a second portion of the dielectric material, the second portion is etched to form a trench, and a metal structure is formed within the trench.

[0003] Special Publication No. 2016-534578

[0004] This disclosure provides a technique for forming a film having an opening.

[0005] A substrate processing method according to one aspect of the present disclosure includes the steps of: preparing a substrate having a resist film in which a first opening is formed; supplying a first raw material containing a first metal-containing precursor, filling the first opening with a first fluidized film containing the metal contained in the first metal-containing precursor at a temperature lower than the boiling point of the first metal-containing precursor, and then curing the first fluidized film to form a first metal-containing film in the first opening; removing the resist film to form a second opening adjacent to the first metal-containing film; supplying a first film-forming gas to form a first film on the side surface of the first metal-containing film; and removing the first metal-containing film to form a third opening adjacent to the first film.

[0006] According to this disclosure, a membrane having an opening can be formed.

[0007] This is a flowchart illustrating a substrate processing method according to the first embodiment. This is a schematic cross-sectional view showing a substrate prepared in step S101. This is a schematic cross-sectional view showing a substrate containing the first metal-containing film after the second opening has been formed. This shows a schematic view of the substrate after the first film has been formed. This is a schematic cross-sectional view showing a substrate after a portion of the first film has been removed. This is a schematic cross-sectional view showing a substrate after the first metal-containing film has been removed. This is a flowchart illustrating an example of steps S102 and S103 shown in Figure 1. This is a schematic diagram showing a substrate in the initial stage where the first fluidized film is attached to the upper surface of the resist film and the side and bottom surfaces of the first opening. This is a schematic cross-sectional view showing a substrate at the stage when the first fluidized film has been filled into the first opening. This is a schematic cross-sectional view showing a substrate containing the first metal-containing film. This is a schematic cross-sectional view showing a substrate after the first metal-containing film on the resist film has been removed. This is a schematic cross-sectional view showing a substrate containing the first metal-containing film after the second opening has been formed. This is a schematic diagram showing an example of the reaction process from the first metal-containing precursor to the generation of the first fluidized film. This is a flowchart illustrating a substrate processing method according to the second embodiment. It schematically shows a substrate after the second film has been deposited. This is a schematic cross-sectional view of a substrate after a portion of the second film has been removed. This is a schematic cross-sectional view of a substrate after the first film has been removed. This is a flowchart illustrating a substrate processing method according to the third embodiment. This is a schematic cross-sectional view of a substrate after the second metal-containing film has been deposited. This is a schematic cross-sectional view of a substrate after the second metal-containing film on the second film has been removed. This is a schematic cross-sectional view of a substrate after the fifth opening has been formed. This is a flowchart illustrating a substrate processing method according to the fourth embodiment. This is a schematic cross-sectional view of a substrate after the third film has been deposited. This is a schematic cross-sectional view of a substrate after a portion of the third film has been removed. This is a schematic cross-sectional view of a substrate after the second film has been removed. This is a schematic diagram showing an example of the configuration of a substrate processing system according to the embodiment. This is a schematic diagram showing an example of the configuration of a substrate processing apparatus according to the embodiment.

[0008] Hereinafter, exemplary embodiments of the present disclosure, not limited to those described herein, will be described with reference to the attached drawings. In all attached drawings, identical or corresponding members or components are denoted by the same or corresponding reference numerals, and redundant descriptions are omitted.

[0009] [Substrate Processing Method] <First Embodiment> A substrate processing method according to a first embodiment will be described with reference to FIGS. 1 to 5. FIG. 1 is a flowchart showing the substrate processing method according to the first embodiment. FIG. 2 is a cross-sectional view schematically showing a substrate 100 for explaining the substrate processing method according to the first embodiment. FIG. 3 is a flowchart showing an example of step S102 and step S103 shown in FIG. 1. FIG. 4 is a cross-sectional view schematically showing the substrate 100 in each step of step S102 and step S103. FIG. 5 is a schematic diagram showing an example of a reaction process from a first metal-containing precursor until a first fluidized film 131 is formed.

[0010] The substrate processing method according to the first embodiment includes steps S101 to S105 shown in FIG. 1. Step S101 includes preparing a substrate 100. The substrate 100 has a resist film 120 in which a first opening 121 is formed.

[0011] FIG. 2A is a cross-sectional view schematically showing the substrate 100 prepared in step S101. As shown in FIG. 2A, the substrate 100 further includes a base film 110. The resist film 120 is formed on the base film 110. In the example shown in FIG. 2A, the first opening 121 has a trench shape recessed from the upper surface of the resist film 120 toward the base film 110. However, the shape of the first opening 121 is not limited to the trench shape.

[0012] The base film 110 includes, for example, an amorphous silicon film. However, the base film 110 may be a film different from the amorphous silicon film. Examples of films different from the amorphous silicon film include single-crystal silicon films, polycrystalline silicon films, silicon oxide films, silicon nitride films, hafnium oxide films, zirconium oxide films, carbon-containing films, ITO (Indium Tin Oxide) films, IGZO films, tungsten films, titanium films, titanium nitride films, and molybdenum films. Further, the base film 110 may include other films such as a backside anti-reflection film. The type of the base film 110 can be appropriately selected in consideration of, for example, the etching selectivity for a first metal-containing film 132 and a first film 140 described later.

[0013] The resist film 120 is formed from a photoresist composition. The photoresist composition is, for example, a chemically amplified type. The resist film 120 may or may not have functional groups that bond with metal M in step S102 described later. The functional groups can be general, but for example, carboxyl groups, phenyl groups, or acrylic groups. The resist film 120 may be a negative-type photoresist film or a positive-type photoresist film. Alternatively, the resist film 120 may be a resist film formed using NIL (Nano-Imprint Lithography) instead of a photoresist composition.

[0014] Step S101 may include forming a resist film 120 on the underlayer film 110 using a coating method such as spin coating. Alternatively, step S101 may include sequentially performing an exposure treatment and a development treatment on the resist film 120 formed on the underlayer film 110 to form a first opening 121 in the resist film 120. Furthermore, step S101 may include transporting the substrate 100 having the resist film 120 with the first opening 121 formed into the processing container 10.

[0015] After step S101, steps S102 and S103 are carried out in order. Step S102 includes forming a first metal-containing film 132. Step S103 includes forming a second opening 133. Steps S102 and S103 will be described in detail with reference to Figures 3 to 5.

[0016] As shown in Figure 3, step S102 includes, for example, steps S102a and S102b. Step S102a includes supplying a first raw material containing a first metal-containing precursor to fill the first opening 121 with a first fluidized film 131 containing the metal M contained in the first metal-containing precursor. Step S102a may also include filling the first fluidized film 131 such that the upper surface of the first metal-containing film 132 is located above the upper surface of the resist film 120.

[0017] In this embodiment, in step S102a, a raw material gas containing a first metal-containing precursor is supplied as the first raw material. Step S102a is an example of a step in which a raw material gas containing a first metal-containing precursor is supplied. In this case, for example, step S102a can be performed using the first processing apparatus PM1 described later. However, the method of supplying the first raw material is not limited to supplying a raw material gas. For example, a fluid raw material containing a first metal-containing precursor may be supplied as the first raw material. In this case, for example, the fluid raw material is applied using a coating method such as a spin coating method. The following explanation will use the case where a raw material gas is supplied as the first raw material as an example, but the same applies when a fluid raw material is supplied as the first raw material.

[0018] In step S102a, the first fluidized film 131 is filled into the first opening 121 at a temperature lower than the boiling point of the first metal-containing precursor. Specifically, the temperature of the substrate 100 in step S102a is lower than the boiling point of the first metal-containing precursor. A temperature lower than the boiling point of the first metal-containing precursor is, for example, a temperature below room temperature. However, the temperature of the substrate 100 in step S102a may be higher than room temperature, as long as it is lower than the boiling point of the first metal-containing precursor.

[0019] When the first raw material is supplied into the processing container 10, the pressure inside the processing container 10 is reduced to a pressure lower than atmospheric pressure (for example, a vacuum atmosphere). That is, the boiling point of the first metal-containing precursor is the boiling point under the pressure inside the processing container 10 when the first raw material is supplied. For example, if the pressure inside the processing container 10 is reduced to a pressure lower than atmospheric pressure, the boiling point of the first metal-containing precursor refers to the boiling point under the pressure inside the processing container 10 after the reduction in pressure, not the boiling point under atmospheric pressure.

[0020] The first metal-containing precursor contains metal M. The first metal-containing precursor is, for example, an amino metal compound. The amino metal compound is a compound containing metal M and two or more amino groups bonded to metal M. Examples of amino metal compounds include bis-DMADMS (Bis(dimethylamino)dimethylsilane), TDMAS (Tris(dimethylamino)silane), BTBAS (Bis(t-butylamino)silane), and BDE. AS (Bis(diethylamino)silane), Bis-DMADMSn (Bis(dimethylamino)dimethyltin), TDMASn (Tetrakis(dimethylamino)tin), TDMAHf(Tetrakis(dime) thylamino)hafnium), TDMATi (Tetrakis(dimethylamino)titanium), TDMAGe(Tris(dimethylamino)germanium), Bis-BTMSG(Bis[bis(trimethylsi lyl)amide] germanium), TDMAZr (Tetrakis(dimethylamino)zirconium), BTBIBDMAW (Bis(tert-butylimino)bis(dimethylamino)tungsten), Al(NMe ２ ) ３ (Tris(dimethylamino)aluminum), Al ２ (NMe ２ ) ６ (Tris(dimethylamino)alane dimer) is used.

[0021] Metal M may include metalloids such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te). Examples of metal M include Si, Ge, hafnium (Hf), tin (Sn), titanium (Ti), zirconium (Zr), tungsten (W), or aluminum (Al). However, metal M may be a different metal from these.

[0022] Referring to Figure 5, an example of the reaction process from the first metal-containing precursor to the formation of the first fluidized membrane 131 will be explained. Figure 5(a) shows bis-DMADMS, an example of the first metal-containing precursor. Figure 5(b) shows an example of silanol, an intermediate produced from the first metal-containing precursor. Figure 5(c) shows polydimethylsiloxane, an example of the first fluidized membrane 131. Figure 5(d) shows octamethylcyclotetrasiloxane, another example of the first fluidized membrane 131.

[0023] However, the first metal-containing precursor is not limited to the compound shown in Figure 5(a). The first metal-containing precursor may be an amino metal compound containing a metal M different from Si, such as Ge, Hf, Sn, Ti, Zr, W, and Al. Furthermore, when the first metal-containing precursor is an amino metal compound, the amino group contained in the amino metal compound includes, for example, a methyl group, as shown in Figure 5(a). However, the amino group contained in the amino metal compound may contain a hydrogen (H) atom or an organic group different from a methyl group. An organic group different from a methyl group is, for example, an alkyl group other than a methyl group. Furthermore, the first metal-containing precursor may be a compound containing a metal M different from these metals.

[0024] The intermediate produced from the first metal-containing precursor is not limited to the silanol shown in Figure 5(b). The intermediate produced from the first metal-containing precursor can be appropriately changed depending on the type of first metal-containing precursor. The polysiloxane as the first fluidized membrane 131 is not limited to the polydimethylsiloxane shown in Figure 5(c) and the octamethylcyclotetrasiloxane shown in Figure 5(d). The polysiloxane as the first fluidized membrane 131 may be other polysiloxanes such as hexamethylcyclotrisiloxane or decamethylcyclopentasiloxane. The first fluidized membrane 131 can be appropriately changed depending on the type of intermediate produced from the first metal-containing precursor.

[0025] When the first raw material is supplied into the processing container 10, bis-DMADMS and H shown in Figure 5(a) are produced. ２ O molecules react with H to produce, for example, silanol and dimethylamine as shown in Figure 5(b). ２O molecules may be water vapor (H ２ O molecules) contained in the additional gas supplied into the processing vessel 1 together with the first raw material. Further, H ２ O molecules may be H ２ O molecules contained in the resist film 120. Furthermore, H ２ O molecules may be H ２ O molecules remaining in the processing vessel 1 before the first raw material is supplied, or H ２ O molecules that enter the processing vessel 1 from the outside when the first raw material is supplied.

[0026] After bis-DMADMS reacts with H ２ O molecules to generate silanol, a dehydration condensation reaction between a plurality of silanols occurs, and polysiloxanes such as polydimethylsiloxane shown in Fig. 5(c) and octamethylcyclotetrasiloxane shown in Fig. 5(d) are generated. On the other hand, H eliminated in the dehydration condensation reaction of silanol ２ O molecules react with bis-DMADMS in the first raw material remaining in the processing vessel 10. Thereby, new silanol is generated. That is, when the reaction between bis-DMADMS and H ２ O molecules starts, polysiloxanes such as those shown in Fig. 5(c) and Fig. 5(d) are continuously generated in the processing vessel 10 regardless of whether new H ２ O molecules are supplied or not.

[0027] The polysiloxane produced through the reaction process shown in Figure 5 adheres to the upper surface of the resist film 120 and to the side and bottom surfaces of the first opening 121, thereby forming the first fluidized film 131. The side surface of the first opening 121 is the side surface of the resist film 120. The bottom surface of the first opening 121 is the upper surface of the undercoat film 110. Since the temperature of the substrate 100 in step S102a is lower than the boiling point of bis-DMADMS, the first fluidized film 131 contains liquid-phase polysiloxanes such as liquid-phase polydimethylsiloxane and liquid-phase octamethylcyclotetrasiloxane. Therefore, the first fluidized film 131 has fluidity during the period in which step S102a is carried out. Even if the first metal-containing precursor is a metal-containing compound different from bis-DMADMS, the first fluidized film 131 contains a liquid-phase compound produced using the first metal-containing precursor as a starting material.

[0028] Figure 4A is a schematic diagram showing the substrate 100 in its initial stage, where the first fluidized film 131 is attached to the upper surface of the resist film 120 and to the side and bottom surfaces of the first opening 121. Figure 4B is a schematic cross-sectional view showing the substrate 100 at the stage when the first fluidized film 131 has filled the first opening 121. In step S102a, the temperature of the substrate 100 is set to a temperature lower than the boiling point of the first metal-containing precursor, which suppresses the bonding between the metal M contained in the first metal-containing precursor and the functional groups contained in the resist film 120. That is, the penetration of metal M into the resist film 120 is limited. Therefore, as shown in Figure 4A, in the initial stage, the first fluidized film 131 is formed on the upper surface of the resist film 120 and to the side and bottom surfaces of the first opening 121. Also, as a result of limiting the penetration of metal M into the resist film 120, as shown in Figure 4B, the first fluidized film 131 is deposited on the outside of the resist film 120. As a result, the first fluidized membrane 131 is filled into the first opening 121. The first fluidized membrane 131 is filled into the first opening 121 while maintaining its fluidity. Therefore, voids and seams in the membrane can be reduced compared to the case where a solid-phase compound is embedded in the first opening 121. This makes it possible to form a conformal first fluidized membrane 131.

[0029] Step S102b is performed after step S102a. Step S102b includes supplying an oxidizing gas into the processing container 10 and curing the first fluidized film 131 filled in the first opening 121 to form a first metal-containing film 132 on the first opening 121. In step S102b as well, the pressure inside the processing container 10 may be reduced to a pressure lower than atmospheric pressure (for example, a vacuum atmosphere). Step S102b is performed, for example, using the first processing apparatus PM1 described later.

[0030] Examples of oxidizing agents contained in oxidizing gases include O ２ Molecules, ozone (O ３ ) molecule, CO ２ molecule, SO ２ molecule, or O ２ Plasma, CO ２ Plasma, SO ２ Plasma can be used. Figure 4C is a schematic cross-sectional view showing a substrate 100 including a first metal-containing film 132. As the first fluidized film 131 is cured by the oxidizing agent, the first metal-containing film 132 is formed on the first opening 121, as shown in Figure 4C. As mentioned above, since voids and seams in the first fluidized film 131 are reduced, voids and seams in the first metal-containing film 132 obtained by curing the first fluidized film 131 are also reduced. That is, a conformal first metal-containing film 132 can be formed in step S102b. If the upper surface of the first fluidized film 131 is located above the upper surface of the resist film 120, the upper surface of the first metal-containing film 132 is also located above the upper surface of the resist film 120.

[0031] The first metal-containing film 132 is a film containing metal M and oxygen (O). The first metal-containing film 132 may further contain H atoms or organic groups derived from the first metal-containing precursor. The organic group derived from the first metal-containing precursor is, for example, an alkyl group. If the first fluidized film 131 contains polysiloxane, the first metal-containing film 132 is a silicon oxide-like film.

[0032] If the first metal-containing precursor is a compound containing Sn, such as bis-DMADMSn and TDMASn, the first metal-containing film 132 is a tin oxide-like film. If the first metal-containing precursor is a compound containing Hf, such as TDMAHf, the first metal-containing film 132 is a hafnium oxide-like film. If the first metal-containing precursor is a compound containing Ti, such as TDMATi, the first metal-containing film 132 is a titanium oxide-like film. If the first metal-containing precursor is a compound containing Ge, such as TDMAGe, the first metal-containing film 132 is a germanium oxide-like film. If the first metal-containing precursor is a compound containing Zr, such as TDMAZr, the first metal-containing film 132 is a zirconium oxide-like film. If the first metal-containing precursor is a compound containing W, such as BTBIBDDMAW, the first metal-containing film 132 is a tungsten oxide-like film. The first metal-containing precursor is Al(NMe ２ ) ３ When the compound contains Al, the first metal-containing film 132 is an aluminum oxide-like film.

[0033] Furthermore, after step S102a, for example, the processing container 10 is opened to the atmosphere, and O is released into the processing container 10. ２ The first fluidized film 131 can also be cured by introducing molecules. That is, by introducing O into the processing container 10 ２ The first flow film 131 can be cured by molecules to obtain the first metal-containing film 132. In this case, the supply of oxidizing gas into the processing container 10 can be omitted in step S102b.

[0034] Step S102 may include repeating steps S102a and S102b multiple times. The number of times steps S102a and S102b are repeated can be appropriately changed depending on the amount of the first metal-containing film 132 that is deposited.

[0035] Step S102 may include supplying a purge gas into the processing container 10 after step S102b. The purge gas discharges any remaining first metal-containing precursor from the processing container 10 to the outside of the processing container 10. The purge gas also discharges any excess first metal-containing precursor physically adsorbed on the surface of the first metal-containing film 132 to the outside of the processing container 10. The purge gas may be, for example, nitrogen (N ２ It is either a gas or argon (Ar) gas.

[0036] An example of the processing conditions for step S102 is as follows: • Flow rate of the first raw material (raw material gas): 1 sccm to 100 sccm • Flow rate of the additive gas: 1 sccm to 100 sccm • Flow rate of the oxidizing gas: 100 sccm to 1000 sccm • Temperature of the substrate 100: -20°C to 40°C (however, not exceeding the boiling point of the first metal-containing precursor under the pressure inside the processing container 10) • Temperature inside the processing container 10 excluding the substrate 100: 30°C to 200°C • Processing pressure: 1 Torr to 500 Torr (133 Pa to 66660 Pa) • Processing time: 60 seconds to 1200 seconds

[0037] Step S103 is performed after step S102. As shown in Figure 3, step S103 includes, for example, steps S103a and S103b. Step S103a includes removing the first metal-containing film 132 on the resist film 120 to expose the resist film 120. Step S103a is performed, for example, using the second processing apparatus PM2, which will be described later.

[0038] Step S103a is performed when, in step S102, the first metal-containing film 132 is formed such that its upper surface is located above the upper surface of the resist film 120. Therefore, if, at the stage when step S102 is performed, the upper surface of the first metal-containing film 132 and the upper surface of the resist film 120 are on the same plane and the resist film 120 is exposed, step S103a can be omitted.

[0039] Figure 4D is a schematic cross-sectional view of the substrate 100 after the first metal-containing film 132 on the resist film 120 has been removed. As shown in Figure 4D, when the first metal-containing film 132 on the resist film 120 is removed, the upper surface of the first metal-containing film 132 is located on the same plane as, for example, the upper surface of the resist film 120.

[0040] In step S103a, the first metal-containing film 132 on the resist film 120 is etched to expose the resist film 120. The etching gas used for etching the first metal-containing film 132 on the resist film 120 is, for example, a gas containing halogens such as fluorine (F), chlorine (Cl), or bromine (Br), or a noble gas (helium (He) gas, Ar gas, xenon (Xe) gas, krypton (Kr) gas). For example, a gas containing F is CF ４ Gas or SF ６ It is a gas. A gas containing Cl is, for example, Cl ２ Gas or BCl ３ It is a gas. A gas containing Br is, for example, HBr gas. The etching gas may be a single gas or a mixed gas. The etching gas can be appropriately selected according to the composition of the first metal-containing film 132.

[0041] If the first metal-containing film 132 is a silicon oxide-like film, the etching gas is, for example, CF ４ A gas can be used. When the first metal-containing film 132 is a tin oxide-like film, the etching gas can be, for example, a mixed gas of HBr gas and Ar gas, or CF ４ A gas can be used. If the first metal-containing film 132 is a hafnium oxide-like film, the etching gas can be, for example, Cl ２ Gas and BCl ３ Gas mixture, SF ６ Gas, or CF ４ Gas and H ２ A mixed gas can be used. When the first metal-containing film 132 is a titanium oxide-like film or a tungsten oxide-like film, the etching gas can be, for example, Cl ２ Gas and BCl ３A mixed gas can be used. When the first metal-containing film 132 is a germanium oxide-like film, a zirconium oxide-like film, or an aluminum oxide-like film, an etching gas capable of removing these films can be appropriately selected.

[0042] In step S103a, the exposure of the upper surface of the resist film 120 can be determined, for example, based on a detection signal output from the OES (Optical Emission Spectrometer) of the second processing apparatus PM2. In step S103a, for example, if the OES detects a carbon component contained in the resist film 120, the etching process of the first metal-containing film 132 is stopped.

[0043] Step S103b is performed after step S103a. Step S103b includes removing the resist film 120. Specifically, the resist film 120 with its upper surface exposed is etched while leaving the first metal-containing film 132 in the first opening 121 of the resist film 120. As a result of the removal of the resist film 120, a second opening 133 adjacent to the first metal-containing film 132 is formed. Step S103b is performed, for example, using a third processing apparatus PM3 described later.

[0044] For example, a gas containing O can be used as the etching gas for etching the resist film 120. ２ Gas, CO ２ Gas, SO ２ The etching gas is either a gas or a COS gas. The etching gas used for etching the resist film 120 can be appropriately selected according to the composition of the resist film 120 and its selectivity ratio with the first metal-containing film 132.

[0045] Figures 2B and 4E are schematic cross-sectional views showing the substrate 100 including the first metal-containing film 132 after the second opening 133 has been formed. The opening pattern formed by the second opening 133 (hereinafter referred to as the "second opening pattern") is an inverted opening pattern of the opening pattern formed by the first opening 121 of the resist film 120 (hereinafter referred to as the "first opening pattern"). That is, the second opening 133 is located where the resist film 120 was, and the first metal-containing film 132 is located where the first opening 121 of the resist film 120 was. In the example shown in Figures 2B and 4E, the second opening 133 has a trench shape that is recessed from the upper surface of the first metal-containing film 132 toward the underlayer film 110. However, the shape of the second opening 133 is not limited to a trench shape.

[0046] By performing steps S102 and S103, the second opening pattern can be inverted relative to the first opening pattern. Therefore, the roughness of the first opening pattern is not reflected in the second opening pattern. As a result, by performing steps S102 and S103, a second opening pattern with reduced roughness compared to the first opening pattern can be obtained. Furthermore, the first metal-containing film 132 is located where the first opening 121 of the resist film 120 was formed. Therefore, even if a bridge defect exists within the first opening 121 of the resist film 120, the bridge defect can be covered by the first metal-containing film 132. This makes it possible to obtain a second opening pattern with fewer bridge defects.

[0047] Referring again to Figures 1 and 2, the steps from step S104 onward will be explained. As shown in Figure 1, step S104 is performed after step S103. Step S104 includes supplying a first film-forming gas and forming a first film 140 on the side surface 132s of the first metal-containing film 132. Step S104 is performed, for example, using the fourth processing apparatus PM4, which will be described later.

[0048] Figure 2C schematically shows the substrate 100 after the first film 140 has been deposited. In the example shown in Figure 2C, the first film 140 is deposited not only on the side surface 132s of the first metal-containing film 132, but also on the top surface of the first metal-containing film 132 and the bottom surface of the second opening 133. The bottom surface of the second opening 133 is the top surface of the undercoat film 110.

[0049] In step S104, the first film 140 is formed using, for example, CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition). The first film 140 is a film that exhibits etching selectivity for the first metal-containing film 132. The first film 140 may contain, for example, a metal M such as Si. The first film 140 may also contain other elements such as O and nitrogen (N). However, the first film 140 is not limited to the above, as long as it exhibits etching selectivity for the first metal-containing film 132.

[0050] The first film-forming gas includes, for example, a raw material gas containing a metal M such as Si, and a reaction gas containing other elements such as O or N, which reacts with the raw material gas. When the first film 140 is formed using the CVD method, the raw material gas and reaction gas in the first film-forming gas can be supplied at the same time. When the first film 140 is formed using the ALD method, the raw material gas and reaction gas in the first film-forming gas can be supplied alternately.

[0051] In step S104, after forming the first film 140, the portion of the first film 140 formed on the upper surface of the first metal-containing film 132 and the bottom surface of the second opening 133 (hereinafter referred to as "a portion of the first film 140") can be removed. Figure 2D is a schematic cross-sectional view showing the substrate 100 after a portion of the first film 140 has been removed. As shown in Figure 2D, after a portion of the first film 140 has been removed, the portion of the first film 140 formed on the side surface 132s of the first metal-containing film 132 remains. This allows the first metal-containing film 132 to be exposed from the first film 140. Furthermore, it is possible to prevent the height of the first film 140 from varying depending on its position in the in-plane direction.

[0052] The etching gas used to remove a portion of the first film 140 is, for example, CH２ F ２ Gas, CHF ３ Gas, CH ３ The etching gas is F gas or other hydrofluorocarbon gas. The etching gas may be a single gas or a mixture of gases.

[0053] An example of the processing conditions for step S104 is as follows. Note that in the following, Si is used as the first film 140. ３ N ４ An example of film formation, where the source gas is SiCl ４ As a gas, the reaction gas is NH ３ This is an example using gases. • Flow rate of raw material gas in the first film formation gas: 10 sccm to 100 sccm • Flow rate of reaction gas in the first film formation gas: 10 sccm to 100 sccm • Temperature of substrate 100: 300°C to 700°C • Processing pressure: 10 mTorr to 10 Torr (1.3 Pa to 1333 Pa) • Processing time: 5 seconds to 100 seconds

[0054] Step S105 is performed after step S104. Step S105 includes removing the first metal-containing film 132 and forming the third opening 141. Step S105 is performed, for example, using the second processing apparatus PM2 described later.

[0055] Figure 2E is a schematic cross-sectional view of the substrate 100 after the first metal-containing film 132 has been removed. As shown in Figure 2E, the third opening 141 is adjacent to the first film 140. In the example shown in Figure 2E, the third opening 141 has a trench shape that is recessed from the upper surface of the first film 140 toward the underlying film 110. However, the shape of the third opening 141 is not limited to a trench shape.

[0056] As shown in Figure 2E, the opening width W3 of the third opening 141 is shorter than the opening width W2 of the second opening 133 (see Figure 2B). That is, by performing step S105, the distance between the first films 140 located on both sides of the third opening 141 can be made shorter than the distance between the first metal-containing films 132 located on both sides of the second opening 133. By performing steps S101 to S105, a self-aligning multi-patterning process can be applied to the substrate 100.

[0057] The etching gas used to remove the first metal-containing film 132 in step S105 may be the etching gas exemplified in step S103a. As described above, the first film 140 has etching selectivity with respect to the first metal-containing film 132. Therefore, by supplying an etching gas to the substrate 100 to remove the first metal-containing film 132, the first metal-containing film 132 can be selectively removed from the first film 140.

[0058] As described above, according to this embodiment, a first film 140 having a third opening 141 can be formed on the base film 110.

[0059] Furthermore, according to this embodiment, a portion of the undercoat 110 is not removed during each process leading up to the formation of the third opening 141. Therefore, even if the third opening 141 is not formed according to the design specifications and it becomes necessary to repeat the previous processes, the first opening 121 to the third opening 141 can be reformed without replacing the substrate 100. This reduces costs compared to the case where each opening 121, 133, and 141 is reformed after replacing the substrate 100. In addition, the time required to reform each opening 121, 133, and 141 can be shortened.

[0060] Incidentally, there are cases where it is required to form an opening with an extremely short opening width of about a few nanometers. In this case, high processing accuracy is required to form an extremely fine opening, but there is a high possibility that the opening will not be formed according to the design value in a single process. This embodiment, which can reform the opening without replacing the substrate 100, is particularly suitable for substrate processing methods that form such extremely fine openings as described above.

[0061] Furthermore, after step S105, a portion of the undercoat 110 can be removed using the first film 140 as a mask. Removing a portion of the undercoat 110 may be done using any of the first processing apparatus PM1 to the fourth processing apparatus PM4 described later, or it may be done using a processing apparatus other than the first processing apparatus PM1 to the fourth processing apparatus PM4.

[0062] The etching gas used to remove a portion of the undercoat 110 can be appropriately selected according to the composition of the undercoat 110 and its selectivity ratio with the first film 140. The etching gas may be a single gas or a mixed gas. Furthermore, after removing a portion of the undercoat 110, the first film 140 can be removed.

[0063] <Second Embodiment> The substrate processing method according to the second embodiment will be described with reference to Figures 6 and 7. Figure 6 is a flowchart showing the substrate processing method according to the second embodiment. Figure 7 is a schematic cross-sectional view showing a substrate 100A for explaining the substrate processing method according to the second embodiment. For the sake of explanation, the position and width of the first film 140 shown in Figure 7 are different from the position and width of the first film 140 shown in Figure 2.

[0064] The substrate processing method according to the second embodiment includes steps S201 to S207 shown in Figure 6. Here, steps S201 to S205 may be the same as steps S101 to S105 in the first embodiment. Therefore, the explanation of steps S201 to S205 will be omitted.

[0065] Step S206 is performed after step S205. Step S206 includes supplying a second film-forming gas to form the second film 150 on the side surface 140s of the first film 140. Step S205 is performed, for example, using the fourth processing apparatus PM4 described later.

[0066] Figure 7A schematically shows the substrate 100A after the second film 150 has been deposited. In the example shown in Figure 7A, the second film 150 is deposited not only on the side surface 140s of the first film 140, but also on the top surface of the first film 140 and the bottom surface of the third opening 141. The bottom surface of the third opening 141 is the top surface of the undercoat film 110.

[0067] In step S205, the second film 150 is formed in the same manner as the first film 140, for example, using a CVD method or an ALD method. The second film 150 is a film that exhibits etching selectivity to the first film 140. The second film 150 may contain, for example, a metal M such as Si. The second film 150 may also contain other elements such as O and N. However, the second film 150 is not limited to the above, as long as it exhibits etching selectivity to the first film 140.

[0068] The second film-forming gas includes, for example, a source gas containing a metal M such as Si, and a reaction gas containing other elements such as O or N, which reacts with the source gas. When the second film 150 is formed using the CVD method, the source gas and reaction gas in the second film-forming gas can be supplied at the same time. When the second film 150 is formed using the ALD method, the source gas and reaction gas in the second film-forming gas can be supplied alternately.

[0069] In step S206, after the second film 150 is formed, the portion of the second film 150 that has been formed on the upper surface of the first film 140 and the bottom surface of the third opening 141 (upper surface of the underlayer film 110) (hereinafter referred to as "part of the second film 150") can be removed. Figure 7B is a schematic cross-sectional view showing the substrate 100A after a portion of the second film 150 has been removed. As shown in Figure 7B, after a portion of the second film 150 has been removed, the portion of the second film 150 formed on the side surface 140s of the first film 140 remains. This allows the upper surface of the first film 140 to be exposed from the second film 150.

[0070] The etching gas used to remove a portion of the second film 150 is, for example, Cl ２ Gas, BCl ３ The etching gas is either a gas or Ar gas. The etching gas may be a single gas or a mixture of gases.

[0071] An example of the processing conditions for step S206 is as follows. Note that in the following, TiO is used as the second film 150. ２This is an example of film deposition, where the source gas is TDMATi gas and the reaction gas is water vapor. • Flow rate of source gas in the second deposition gas: 10 sccm to 100 sccm • Flow rate of reaction gas in the second deposition gas: 10 sccm to 100 sccm • Temperature of substrate 100A: 50°C to 400°C • Processing pressure: 10 mTorr to 10 Torr (1.3 Pa to 1333 Pa) • Processing time: 5 seconds to 100 seconds

[0072] Step S207 is performed after step S206. Step S207 includes removing the first film 140 and forming the fourth opening 151. Step S207 is performed, for example, using the second processing apparatus PM2 described later.

[0073] Figure 7C is a schematic cross-sectional view of the substrate 100A after the first film 140 has been removed. As shown in Figure 7C, the fourth opening 151 is adjacent to the second film 150. In the example shown in Figure 7C, the fourth opening 151 has a trench shape that is recessed from the upper surface of the second film 150 toward the underlayer film 110. However, the shape of the fourth opening 151 is not limited to a trench shape.

[0074] As shown in Figure 7C, the opening width W4 of the fourth opening 151 is shorter than the opening width W3 of the third opening 141 (see Figure 2E). That is, by performing step S207, the distance between the second films 150 located on both sides of the fourth opening 151 can be made shorter than the distance between the first films 140 located on both sides of the third opening 141. By performing steps S201 to S207, a self-aligned multi-patterning process can be applied to the substrate 100A.

[0075] In step S207, the etching gas used to remove the first film 140 is, for example, CH ２ F ２ Gas, CH ３ F gas, CHF ３The etching gas is a gas or other hydrofluorocarbon-based gas. The etching gas may be a single gas or a mixed gas. As described above, the second film 150 has etching selectivity with respect to the first film 140. Therefore, by supplying an etching gas to the substrate 100A to remove the first film 140, the first film 140 can be selectively removed with respect to the second film 150.

[0076] As described above, according to this embodiment, a second film 150 having a fourth opening 151 can be formed on the base film 110.

[0077] In the second embodiment as well, a portion of the undercoat 110 is not removed during each process leading up to the formation of the fourth opening 151. Therefore, even if the fourth opening 151 is not formed according to the design specifications and it becomes necessary to repeat the previous processes, the openings 121, 133, 141, and 151 can be reshaped without replacing the substrate 100A. This makes it possible to form a fourth opening 151 with an opening width W4 shorter than the opening width W3 of the third opening 141, and to shorten the time required to reshape the openings 121, 133, 141, and 151.

[0078] Furthermore, after step S207, the second film 150 can be used as a mask to remove a portion of the base film 110. Alternatively, after removing a portion of the base film 110, the second film 150 can be removed.

[0079] <Third Embodiment> The substrate processing method according to the third embodiment will be described with reference to Figures 8 and 9. Figure 8 is a flowchart showing the substrate processing method according to the third embodiment. Figure 9 is a schematic cross-sectional view showing a substrate 100B for illustrating the substrate processing method according to the third embodiment.

[0080] The substrate processing method according to the third embodiment includes steps S301 to S309 shown in Figure 8. Here, steps S301 to S305 may be the same as steps S101 to S105 in the first embodiment. Also, steps S306 and S307 may be the same as steps S206 and S207 in the second embodiment. Therefore, the explanation of steps S301 to S307 is omitted.

[0081] Step S308 is performed after step S307. Step S308 includes forming a second metal-containing film 162 on the fourth opening 151. Specifically, step S308 includes supplying a second raw material containing a second metal-containing precursor to fill the fourth opening 151 with a second fluidized film 161 containing the metal M contained in the second metal-containing precursor at a temperature lower than the boiling point of the second metal-containing precursor. Step S308 also includes forming a second metal-containing film 162 on the fourth opening 151 by curing the second fluidized film 161 after filling the fourth opening 151 with the second fluidized film 161. Step S308 is performed, for example, using the first processing apparatus PM1 described later.

[0082] In step S308, the step of filling the fourth opening 151 with the second fluidized membrane 161 may be the same as in step S102a shown in Figure 3, except that the membrane to be filled is the second fluidized membrane 161. That is, an amino metal compound containing the metal M listed in the first metal-containing precursor can be used as the second metal-containing precursor. Also, the metal M contained in the second metal-containing precursor may be any of the metals listed as the metal M contained in the first metal-containing precursor. As the second raw material, a raw material gas may be used, or a raw material with fluidity may be used.

[0083] In step S308, the step of forming the second metal-containing film 162 on the fourth opening 151 may be the same as in step S102b shown in Figure 3, except that the film to be formed is the second metal-containing film 162. That is, the oxidizing agent or O introduced into the processing container 10 ２Using molecules, the second fluidized film 161 can be cured, and a second metal-containing film 162 can be formed on the fourth opening 151. The second metal-containing film 162 may be a silicon oxide-like film, a tin oxide-like film, a hafnium oxide-like film, a titanium oxide-like film, a germanium oxide-like film, a zirconium oxide-like film, a tungsten oxide-like film, or an aluminum oxide-like film, similar to the first metal-containing film 132.

[0084] Figure 9A is a schematic cross-sectional view of the substrate 100B after the second metal-containing film 162 has been formed. As shown in Figure 9A, by curing the second fluidized film 161, a second metal-containing film 162 is obtained that covers at least the sides of the second film 150. In the example shown in Figure 9A, the upper surface of the second metal-containing film 162 is located above the upper surface of the second film 150.

[0085] Step S309 is performed after step S308. Step S309 includes removing the second film 150 and forming a fifth opening 163. The fifth opening 163 is adjacent to the second metal-containing film 162. The fifth opening 163 has a trench shape that is recessed from the upper surface of the second metal-containing film 162 toward the base film 110. However, the shape of the fifth opening 163 is not limited to a trench shape.

[0086] In this embodiment, in step S308, the upper surface of the second metal-containing film 162 is formed to be above the upper surface of the second film 150. Therefore, in step S309, prior to forming the fifth opening 163, the second metal-containing film 162 on the second film 150 is removed. The step of removing the second metal-containing film 162 on the second film 150 is performed, for example, using the second processing apparatus PM2 described later.

[0087] Figure 9B is a schematic cross-sectional view of the substrate 100B after the second metal-containing film 162 on the second film 150 has been removed. As shown in Figure 9B, after the second metal-containing film 162 on the second film 150 has been removed, the upper surface of the second metal-containing film 162 is located on the same plane as the upper surface of the second film 150. This allows the upper surface of the second film 150 to be exposed from the second metal-containing film 162. The step of removing the second metal-containing film 162 on the second film 150 may be the same as step S103a in the first embodiment, except that the film to be removed is the second metal-containing film 162.

[0088] Next, the second film 150 is removed to form the fifth opening 163. The step of forming the fifth opening 163 is performed, for example, using the second processing apparatus PM2 described later. The step of forming the fifth opening 163 may be the same as step S103b shown in Figure 3, except that the film to be removed is the second film 150. By performing steps S301 to S309, a self-aligned multi-patterning process can be applied to the substrate 100B.

[0089] Figure 9C is a schematic cross-sectional view of the substrate 100B after the fifth opening 163 has been formed. The opening pattern formed by the fifth opening 163 (hereinafter referred to as the "fifth opening pattern") is an inverted opening pattern of the opening pattern formed by the fourth opening 151 (hereinafter referred to as the "fourth opening pattern"). That is, the fifth opening 163 is located where the second film 150 was, and the second metal-containing film 162 is located where the fourth opening 151 of the second film 150 was.

[0090] By performing steps S308 and S309, the fifth opening pattern can be inverted relative to the fourth opening pattern. Therefore, the roughness of the fourth opening pattern is not reflected in the fifth opening pattern. As a result, a fifth opening pattern with reduced roughness compared to the fourth opening pattern can be obtained. Furthermore, the second metal-containing film 162 is located where the fourth opening 151 of the second film 150 was formed. Therefore, even if a bridge defect exists within the fourth opening 151 of the second film 150, the bridge defect can be covered by the second metal-containing film 162. This makes it possible to obtain a fifth opening pattern with fewer bridge defects.

[0091] As described above, according to this embodiment, a second metal-containing film 162 having a fifth opening 163 can be formed on the base film 110.

[0092] In the third embodiment as well, a portion of the undercoat 110 is not removed during each process leading up to the formation of the fifth opening 163. Therefore, even if the fifth opening 163 is not formed as designed and it becomes necessary to repeat the previous processes, the openings 121, 133, 141, 151, and 163 can be reformed without replacing the substrate 100B. This shortens the time required to reform the openings 121, 133, 141, 151, and 163.

[0093] Furthermore, after step S309, the second metal-containing film 162 can be used as a mask to remove a portion of the base film 110. After removing a portion of the base film 110, the second metal-containing film 162 can be removed.

[0094] <Fourth Embodiment> The substrate processing method according to the fourth embodiment will be described with reference to Figures 10 and 11. Figure 10 is a flowchart of the substrate processing method according to the fourth embodiment. Figure 11 is a schematic cross-sectional view showing a substrate 100C for illustrating the substrate processing method according to the fourth embodiment.

[0095] The substrate processing method according to the fourth embodiment includes steps S401 to S408 shown in Figure 10. Here, steps S401 to S405 may be the same as steps S101 to S105 in the first embodiment. Also, step S406 may be the same as step S206 in the second embodiment. Therefore, the explanation of steps S401 to S406 will be omitted.

[0096] Step S407 is performed after step S406. Step S407 includes supplying a third film-forming gas to form the third film 170 on the side surface of the second film 150. After the third film 170 is formed, the second film 150 is positioned between the first film 140 and the third film 170. Step S407 is performed, for example, using a fourth processing apparatus PM4, which will be described later.

[0097] Figure 11A is a schematic cross-sectional view showing the substrate 100C after the third film 170 has been deposited. In the example shown in Figure 11A, the third film 170 is deposited not only on the side surface 150s of the second film 150, but also on the top surface of the first film 140, the top surface of the second film 150, and the bottom surface of the fourth opening 151. The bottom surface of the fourth opening 151 is the top surface of the undercoat film 110.

[0098] The third film-forming gas is preferably the same as the first film-forming gas. That is, the third film 170 is preferably the same as the first film 140. By using the same gas as the first film-forming gas, steps S407 and S404 can be performed in the same processing apparatus. As a result, costs can be reduced. However, the third film-forming gas may be a different gas from the first film-forming gas. That is, the third film 170 may be a different film from the first film 140, as long as it is a film that exhibits etching selectivity for the second film 150.

[0099] Step S407 may be the same as step S404 (step S104), except that the supplied film-forming gas is the third film-forming gas. Therefore, a detailed explanation of step S407 is omitted.

[0100] Step S407 may further include removing the portion of the third film 170 that has been deposited on the upper surface of the first film 140 and the upper surface of the second film 150 (hereinafter referred to as "a portion of the third film 170") after the third film 170 has been deposited. Figure 11B is a schematic cross-sectional view showing the substrate 100C after a portion of the third film 170 has been removed. As shown in Figure 11B, after a portion of the third film 170 has been removed, the portion of the third film 170 deposited on the side surface 150s of the second film 150 remains in addition to the first film 140. This allows the upper surface of the second film 150 to be exposed from the first film 140 and the third film 170.

[0101] The etching gas used to remove a portion of the third film 170 is, for example, CH ２ F ２ Gas, CH ３ F gas, CHF ３ The etching gas is a gas or other hydrofluorocarbon gas. The etching gas may be a single gas or a mixture of gases.

[0102] Step S408 is performed after step S407. Step S408 includes removing the second film 150 and forming the sixth opening 171. Step S408 is performed, for example, using the second processing apparatus PM2 described later.

[0103] Figure 11C is a schematic cross-sectional view of the substrate 100C after the second film 150 has been removed. As shown in Figure 11C, the sixth opening 171 is adjacent to the third film 170. In the example shown in Figure 11C, the sixth opening 171 is also adjacent to the first film 140. In the example shown in Figure 11C, the sixth opening 171 has a trench shape that is recessed from the upper surface of the third film 170 toward the underlayer film 110. However, the shape of the sixth opening 171 is not limited to a trench shape.

[0104] As shown in Figure 11C, the opening width W6 of the sixth opening 171 is shorter than the opening width W3 of the third opening 141 (see Figure 2E). That is, by performing steps S407 and S408, the distance between the first film 140 and the third film 170 located on both sides of the sixth opening 171 can be made shorter than the distance between the first films 140 located on both sides of the third opening 141. By performing steps S401 to S408, a self-aligning multi-patterning process can be applied to the substrate 100C.

[0105] In step S408, the etching gas used to remove the second film 150 is, for example, CF ４ Gas, C ４ F ６ Gas, C ４ F ８ It is a gas or other fluorocarbon gas. Note that the second film 150 is, for example, SiO ２ An example of an etching gas in this case is when the second film 150 is TiO2 as illustrated in the second embodiment. ２ In this case, the etching gas exemplified in step S206 may be used. The etching gas may be a single gas or a mixed gas. As described above, the first film 140 and the third film 170 have etching selectivity with respect to the second film 150. Therefore, by supplying an etching gas to the substrate 100B to remove the second film 150, the second film 150 can be selectively removed from the first film 140 and the third film 170.

[0106] As described above, according to this embodiment, a third film 170 having a sixth opening 171 can be formed on the base film 110.

[0107] In the fourth embodiment as well, a portion of the undercoat 110 is not removed during each process leading up to the formation of the sixth opening 171. Therefore, even if the sixth opening 171 is not formed as designed and it becomes necessary to repeat the previous processes, the openings 121, 133, 141, and 171 can be reformed without replacing the substrate 100C. This shortens the time required to reform the openings 121, 133, 141, and 171.

[0108] Furthermore, after step S408, the first film 140 and the third film 170 can be used as masks to remove a portion of the base film 110. After removing a portion of the base film 110, the first film 140 and the third film 170 can be removed.

[0109] [Substrate Processing System] Referring to Figure 12, an example of a substrate processing system PS for carrying out the substrate processing method according to the embodiment will be described. Figure 12 is a schematic diagram showing an example of the configuration of the substrate processing system PS according to the embodiment. In the example shown in Figure 12, the substrate to be processed in the substrate processing system PS is substrate 100. However, the substrate to be processed in the substrate processing system PS may be substrates 100A, 100B, and 100C. Hereinafter, the substrate processing system PS will be simply referred to as the "processing system PS".

[0110] As shown in Figure 12, the processing system PS comprises a first processing unit PM1, a second processing unit PM2, a third processing unit PM3, a fourth processing unit PM4, a vacuum transport chamber VTM, load lock chambers LL1 to LL3, an atmospheric transport chamber LM, load ports LP1 to LP3, and an overall control unit CU. In the example shown in Figure 12, the processing system PS is described as comprising four processing units (the first to fourth processing units PM1 to PM4), three load lock chambers LL1 to LL3, and three load ports LP1 to LP3, but the number of processing units, load lock chambers, and load ports is not limited to this. Furthermore, the processing system PS may include multiple vacuum transport chambers VTM and / or atmospheric transport chambers LM.

[0111] The first to fourth processing units PM1 to PM4 are each connected to the vacuum transfer chamber VTM via gate valves G11 to G14. The first to fourth processing units PM1 to PM4 are configured to reduce the internal pressure to a predetermined level. The first to fourth processing units PM1 to PM4 house the substrate 100 inside and perform the desired processing.

[0112] The vacuum transport chamber VTM is configured to reduce the internal pressure to a predetermined level. The vacuum transport chamber VTM is equipped with a first transport device TR1 capable of transporting the substrate 100 under reduced pressure. The first transport device TR1 transports the substrate 100 from the first processing device PM1 to the fourth processing device PM4 and the load lock chambers LL1 to LL3. The first transport device TR1 has, for example, two transport arms FK11 and FK12 that can move independently.

[0113] Load lock chambers LL1 to LL3 are connected to the vacuum transport chamber VTM via gate valves G21 to G23, respectively. Load lock chambers LL1 to LL3 are also connected to the atmospheric transport chamber LM via gate valves G31 to G33, respectively. Load lock chambers LL1 to LL3 are configured to allow switching between an atmospheric and a vacuum atmosphere inside.

[0114] The atmospheric transport chamber LM has an atmospheric environment inside. Inside the atmospheric transport chamber LM, for example, a downflow of clean air is formed. An aligner AN for aligning the substrate 100 is provided inside the atmospheric transport chamber LM. The aligner AN may be provided outside the atmospheric transport chamber LM. A second transport device TR2 is provided in the atmospheric transport chamber LM. The second transport device TR2 transports the substrate 100 to the load lock chambers LL1 to LL3, load ports LP1 to LP3 and the aligner AN.

[0115] Load ports LP1 to LP3 are provided on the long side walls of the atmospheric transport chamber LM. Carriers C are attached to load ports LP1 to LP3. Carrier C includes a carrier C containing the substrate 100 and an empty carrier C. Carrier C may be, for example, a FOUP (Front Opening Unified Pod).

[0116] The central control unit (CU) may be, for example, a computer. The central control unit (CU) comprises a CPU (Central Processing Unit), RAM (Random Access Memory), ROM (Read Only Memory), and auxiliary storage. The CPU operates based on a program stored in the ROM or auxiliary storage and controls each part of the processing system PS. For example, the central control unit (CU) controls the operation of the first processing unit PM1 to the fourth processing unit PM4, the first transport device TR1, the second transport device TR2, and the gate valves G11 to G14, G21 to G23, and G31 to G33. For example, the central control unit (CU) controls the operation of switching the inside of the load lock chambers LL1 to LL3 between an atmospheric atmosphere and a vacuum atmosphere.

[0117] Next, the operation of the processing system PS will be described. The operation of the processing system PS when implementing the substrate processing method according to the first embodiment will be described below.

[0118] First, the second transport device TR2 removes the substrate 100 from the carrier C, transports the removed substrate 100 to the aligner AN, and exits from the aligner AN. Next, the aligner AN aligns the substrate 100. Then, the second transport device TR2 removes the substrate 100 from the aligner AN, transports the removed substrate 100 to the load lock chamber LL1, and exits from the load lock chamber LL1. Next, the atmosphere inside the load lock chamber LL1 is switched from atmospheric to vacuum. After that, the first transport device TR1 removes the substrate 100 from the load lock chamber LL1 and loads the removed substrate 100 into the first processing device PM1. When the first transport device TR1 loads and unloads the substrate 100 into the first processing device PM1, the pressure inside the vacuum transport chamber VTM is adjusted to exceed the pressure inside the first processing device PM1. For example, the flow rate of the inert gas flowing into the vacuum transport chamber VTM is adjusted so that the pressure inside the vacuum transport chamber VTM exceeds the pressure inside the first processing unit PM1. The same procedure is followed when transporting the substrate 100 from the second processing unit PM2 to the fourth processing unit PM4.

[0119] The first processing apparatus PM1 deposits a first metal-containing film 132 onto a substrate 100, for example. The first processing apparatus PM1 is a film deposition apparatus that performs a film deposition process on the substrate 100 by, for example, the CVD method. In the first processing apparatus PM1, for example, step S102 shown in Figure 1 is performed.

[0120] Next, the first transport device TR1 removes the substrate 100 from the first processing device PM1 and transports the removed substrate 100 to the second processing device PM2.

[0121] The second processing apparatus PM2 removes, for example, the first metal-containing film 132 above the resist film 120 on the substrate 100. The second processing apparatus PM2 is an etching apparatus. In the second processing apparatus PM2, for example, step S103a shown in Figure 3 is performed. In addition, the second processing apparatus PM2 can remove the first metal-containing film 132 exposed from the first film 140 in step S105 shown in Figure 1. Note that in the second processing apparatus PM2, the operation to remove the first metal-containing film 132 exposed from the first film 140 is performed, for example, after the first film 140 has been formed on the substrate 100 in the fourth processing apparatus PM4.

[0122] Next, the first transport device TR1 removes the substrate 100 from the second processing device PM2 and transports the removed substrate 100 to the third processing device PM3.

[0123] The third processing apparatus PM3 removes, for example, the resist film 120 on the substrate 100. The third processing apparatus PM3 is an etching apparatus. In the third processing apparatus PM3, for example, step S103b shown in Figure 3 is performed.

[0124] Next, the first transport device TR1 removes the substrate 100 from the third processing device PM3 and transports the removed substrate 100 to the fourth processing device PM4.

[0125] The fourth processing apparatus PM4 deposits, for example, the first film 140 onto the substrate 100. The fourth processing apparatus PM4 is a film deposition apparatus. In the fourth processing apparatus PM4, for example, step S104 shown in Figure 1 is carried out.

[0126] Next, the first transport device TR1 removes the substrate 100 from the fourth processing device PM4 and transports the removed substrate 100 to the second processing device PM2. The second processing device PM2 removes the first metal-containing film 132 that is exposed from the first film 140.

[0127] Figure 12 shows a first processing unit PM1 to a fourth processing unit PM4 connected via a vacuum transport chamber VTM of a single processing system PS. However, at least one of the first processing unit PM1 to the fourth processing unit PM4 may be provided independently of the other processing units. For example, the first processing unit PM1 may be provided independently of the second processing unit PM2 to the fourth processing unit PM4. In this case, once the film deposition process by the first processing unit PM1 is completed, the substrate 100 may be transported outside the first processing unit PM1. The substrate 100 transported outside the first processing unit PM1 then passes through the vacuum transport chamber VTM and the atmospheric transport chamber LM, and is then transferred to another processing unit, for example, via a carrier C attached to the atmospheric transport chamber LM.

[0128] In the case of implementing the substrate processing method according to the second to fourth embodiments, each processing device in the processing system PS operates to perform the corresponding steps. Also, in the second to fourth embodiments, the first transport device TR1 can be used to load and unload substrates 100A, 100B, and 100C to and from each processing device.

[0129] [Substrate Processing Apparatus] Next, the first processing apparatus PM1 (hereinafter referred to as "substrate processing apparatus PM1") will be described with reference to Figure 13. Figure 13 is a schematic diagram showing an example of the configuration of the substrate processing apparatus PM1 according to the embodiment. In the example shown in Figure 13, the substrate to be processed in the substrate processing apparatus PM1 is substrate 100. However, the substrate to be processed in the substrate processing apparatus PM1 may be substrates 100A, 100B, and 100C.

[0130] Step S102 of the first embodiment can be carried out using the substrate processing apparatus PM1. Alternatively, step S202 of the second embodiment, step S302 and step S308 of the third embodiment, and step S402 of the fourth embodiment may be carried out using the substrate processing apparatus PM1. In the following description, "raw material gas" refers to the raw material gas as the first raw material unless otherwise specified.

[0131] The substrate processing apparatus PM1 includes a processing container 10, a mounting table 20, a first gas supply unit 30, a first temperature adjustment unit 40, and a control unit 50. The substrate processing apparatus PM1 may further include a second gas supply unit 60, a second temperature adjustment unit 70, an exhaust unit 80, a pressure detection unit 91, a first temperature detection unit 92, and a second temperature detection unit 93.

[0132] The processing container 10 is equipped with an outer wall 11 that partitions the internal processing chamber. The outer wall 11 has, for example, a side wall 111, a bottom wall 112, and a top wall 113. The side wall 111 of the processing container 10 is provided with an opening (not shown) for transporting the substrate 100. The opening is opened and closed by a gate valve G11.

[0133] The mounting table 20 is placed inside the processing container 10. The mounting table 20 is configured to support the substrate 100. As the material for the mounting table 20, for example, ceramic materials such as silicon carbide and aluminum nitride can be used.

[0134] The first gas supply unit 30 is configured to supply a raw material gas containing a first metal-containing precursor into the processing container 10. As shown in Figure 13, the first gas supply unit 30 includes a source 31 for supplying the raw material gas containing the first metal-containing precursor, a supply pipe 32 which is a flow path for the raw material gas, a flow rate controller 33 for controlling the flow rate of the raw material gas, and a valve 34 for opening and closing the supply pipe 32. In the third embodiment, if the first metal-containing precursor and the second metal-containing precursor are the same type of compound, the first gas supply unit 30 can supply a raw material gas containing the second metal-containing precursor into the processing container 10. On the other hand, in the third embodiment, if the first metal-containing precursor and the second metal-containing precursor are different types of compounds, the substrate processing apparatus PM1 may further include another gas supply unit configured to supply a raw material gas containing the second metal-containing precursor.

[0135] The first gas supply unit 30 may be configured to supply purge gas into the processing container 10. The first gas supply unit 30 may include a supply pipe 35 which is a flow path for the purge gas, a flow path switching valve 36 connected to the supply pipes 32 and 35, a supply pipe 37 located downstream of the flow path switching valve 36, and a valve 38 for opening and closing the supply pipe 37. The supply pipe 35 is connected to a purge gas supply source (not shown). The flow path switching valve 36 is configured to switch the fluid flowing through the supply pipe 37 from the raw material gas and the purge gas. The supply pipe 37 is connected to the processing container 10, for example, through a gas supply port 112a provided in the bottom wall 112 of the processing container 10. Note that the connection position between the supply pipe 37 and the processing container 10 (i.e., the connection position between the first gas supply unit 30 and the processing container 10) is not limited to the bottom wall 112. The connection position between the supply pipe 37 and the processing container 10 may be the side wall 111 or the top wall 113.

[0136] In Figure 13, the raw material gas and the purge gas are supplied into the processing container 10 through the same gas supply unit (first gas supply unit 30). However, the raw material gas and the purge gas may be supplied into the processing container 10 through different gas supply units.

[0137] The first temperature control unit 40 adjusts the temperature of the mounting table 20. By adjusting the temperature of the mounting table 20 by the first temperature control unit 40, the temperature of the substrate 100 is adjusted. The first temperature control unit 40 may be, for example, a refrigerant flow path that circulates a low-temperature refrigerant supplied from a chiller to cool the mounting table 20. This allows the substrate 100 placed on the mounting table 20 to be cooled to a temperature lower than the boiling point of the first metal-containing precursor. The first temperature control unit 40 adjusts the temperature of the mounting table 20 in accordance with a control signal from the control unit 50.

[0138] The second gas supply unit 60 is configured to supply additive gas and oxidizing gas into the processing container 10. As shown in Figure 13, the second gas supply unit 60 has a supply pipe 61 which is a flow path for the additive gas and oxidizing gas, and a valve 62 which opens and closes the supply pipe 61. The second gas supply unit 60 may also have a flow rate controller (not shown) for controlling the flow rates of the additive gas and oxidizing gas. The supply pipe 61 is connected to a supply source for the additive gas (not shown) and a supply source for the oxidizing gas (not shown). The supply pipe 61 is connected to the processing container 10, for example, through a gas supply port 112b provided in the bottom wall 112 of the processing container 10. Note that the connection position between the supply pipe 61 and the processing container 10 (i.e., the connection position between the second gas supply unit 60 and the processing container 10) is not limited to the bottom wall 112. The connection position between the supply pipe 61 and the processing container 10 may be the side wall 111 or the top wall 113.

[0139] In Figure 13, the additive gas and the oxidizing gas are supplied into the processing container 10 through the same gas supply unit (second gas supply unit 60). However, the additive gas and the oxidizing gas may be supplied into the processing container 10 through different gas supply units.

[0140] The second temperature control unit 70 adjusts the temperature of the outer wall 11 of the processing container 10. The second temperature control unit 70 is, for example, a heater that heats the outer wall 11. This allows the outer wall 11 to be heated, which suppresses the adhesion of the first fluidized film 131 to the outer wall 11 when the raw material gas is supplied into the processing container 10. The second temperature control unit 70 adjusts the temperature of the outer wall 11 in accordance with the control signal from the control unit 50.

[0141] The exhaust unit 80 includes a pressure regulating valve 81 and a vacuum pump 82. The exhaust unit 80 is connected to the processing container 10 through an exhaust port 113a provided in the top wall 113 of the processing container 10. The exhaust unit 80 adjusts the pressure inside the processing container 10 to a desired level in response to a control signal from the control unit 50. Note that the connection position between the exhaust unit 80 and the processing container 10 is not limited to the top wall 113. The connection position between the exhaust unit 80 and the processing container 10 may be the side wall 111 or the bottom wall 112.

[0142] The pressure detection unit 91 is a sensor that detects the pressure inside the processing container 10. The pressure detection unit 91 is provided, for example, in the exhaust unit 80. The first temperature detection unit 92 is a sensor that detects the temperature of the mounting table 20. The first temperature detection unit 92 is provided, for example, in the mounting table 20. The second temperature detection unit 93 is a sensor that detects the temperature of the outer wall 11 of the processing container 10. The second temperature detection unit 93 is provided, for example, in the outer wall 11. When describing the pressure detection unit 91, the first temperature detection unit 92, and the second temperature detection unit 93 without distinction, they may be collectively referred to as "each detection unit".

[0143] The control unit 50 is, for example, a computer and includes a CPU, RAM, ROM, auxiliary storage device, etc. The CPU operates based on a program stored in the ROM or auxiliary storage device and controls the operation of the substrate processing device PM1. The control unit 50 may be located inside or outside the substrate processing device PM1. If the control unit 50 is located outside the substrate processing device PM1, the control unit 50 can control the substrate processing device PM1 by communication means such as wired or wireless.

[0144] The control unit 50 controls the first gas supply unit 30, the first temperature control unit 40, the second gas supply unit 60, and the exhaust unit 80 to execute the corresponding steps. In the first embodiment, the control unit 50 executes step S102. In the second embodiment, the control unit 50 executes step S202. In the third embodiment, the control unit 50 executes steps S302 and S308. In the fourth embodiment, the control unit 50 executes step S402. Furthermore, the control unit 50 may control the second temperature control unit 70 to execute steps S102, S202, S302, S308, and S402.

[0145] The control unit 50 is configured to control the first temperature adjustment unit 40 so that the temperature of the substrate 100 placed on the mounting table 20 is lower than the boiling point of the first metal-containing precursor. This makes it possible to form conformal first fluidized film 131 and first metal-containing film 132.

[0146] When controlling the first temperature adjustment unit 40, the control unit 50 may acquire information from each detection unit and ROM regarding the pressure inside the processing container 10, the boiling point of the first metal-containing precursor under the pressure inside the processing container 10, and the temperature of the mounting stage 20. The control unit 50 may also determine, based on the acquired information, whether the temperature of the substrate 100 is lower than the boiling point of the first metal-containing precursor. In this case, the control unit 50 may consider the temperature of the mounting stage 20 to be the temperature of the substrate 100. Alternatively, the control unit 50 may, for example, refer to information stored in ROM indicating the correspondence between the temperature of the mounting stage 20 and the temperature of the substrate 100, and convert the temperature of the substrate 100 from the temperature of the mounting stage 20.

[0147] The control unit 50 may be configured to control the second temperature adjustment unit 70 so that the temperature of the outer wall 11 of the processing container 10 is equal to or higher than the boiling point of the first metal-containing precursor. This reduces the adhesion of the first fluidized film 131 to the outer wall 11.

[0148] When controlling the second temperature adjustment unit 70, the control unit 50 may acquire information from each detection unit and ROM regarding the pressure inside the processing container 10, the boiling point of the first metal-containing precursor under the pressure inside the processing container 10, and the temperature of the outer wall 11. The control unit 50 may also determine, based on the acquired information, whether the temperature of the outer wall 11 is equal to or greater than the boiling point of the first metal-containing precursor.

[0149] The embodiments disclosed herein should be considered in all respects to be illustrative and not restrictive. The above embodiments may be omitted, replaced, or modified in various ways without departing from the scope and spirit of the appended claims.

[0150] This application claims priority to Japanese Patent Application No. 2025-043798, filed with the Japan Patent Office on 18 March 2025, the entire contents of which are incorporated herein by reference.

[0151] 100, 100A, 100B, 100C Substrate 120 Resist film 131 First fluid film 132 First metal-containing film 140 First film

Claims

1. A substrate processing method comprising: preparing a substrate having a resist film in which a first opening is formed; supplying a first raw material containing a first metal-containing precursor, filling the first opening with a first fluidized film containing the metal contained in the first metal-containing precursor at a temperature lower than the boiling point of the first metal-containing precursor, and then curing the first fluidized film to form a first metal-containing film in the first opening; removing the resist film to form a second opening adjacent to the first metal-containing film; supplying a first film-forming gas to form a first film on the side surface of the first metal-containing film; and removing the first metal-containing film to form a third opening adjacent to the first film.

2. The substrate processing method according to claim 1, wherein the metal contained in the first metal-containing precursor is at least one of silicon, germanium, hafnium, tin, titanium, zirconium, tungsten, and aluminum.

3. A substrate processing method according to claim 1 or 2, further comprising the steps of: supplying a second film-forming gas to form a second film on the side surface of the first film; and removing the first film to form a fourth opening adjacent to the second film.

4. A substrate processing method according to claim 3, further comprising the steps of: supplying a second raw material containing a second metal-containing precursor; filling the fourth opening with a second fluidized film containing the metal contained in the second metal-containing precursor at a temperature lower than the boiling point of the second metal-containing precursor; and then curing the second fluidized film to form a second metal-containing film in the fourth opening; and removing the second film to form a fifth opening adjacent to the second metal-containing film.

5. The substrate processing method according to claim 4, wherein the metal contained in the second metal-containing precursor is at least one of silicon, germanium, hafnium, tin, titanium, zirconium, tungsten, and aluminum.

6. A substrate processing method according to claim 1 or 2, further comprising: supplying a second film-forming gas to form a second film on the side surface of the first film; supplying a third film-forming gas to form a third film on the side surface of the second film; and removing the second film to form a sixth opening adjacent to the third film.

7. The substrate processing method according to claim 6, wherein the third film-forming gas is the same gas as the first film-forming gas, and the third film is the same film as the first film.

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