Substrate treatment method and substrate treatment device

Abstract

To improve the processability of a photoresist film in EUV exposure.SOLUTION: This substrate treatment method includes a step a) and a step b). In step a), a substrate having a metal-oxide-containing photoresist film formed on the surface thereof is disposed within a chamber. In step b), silicon-containing gas is supplied into the chamber to replace the metal constituting the metal oxide contained in the photoresist film with silicon.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] Various aspects and embodiments of the present disclosure relate to substrate processing methods and substrate processing apparatus. [Background technology]

[0002] The following Patent Document 1 discloses a method for producing a high-silicon steel strip in a continuous line, which is characterized by continuously subjecting a steel strip to a siliconization treatment at a temperature of 1023 to 1200°C by chemical vapor deposition in a non-oxidizing gas atmosphere containing 5 to 35% SiCl4 by molar fraction, then subjecting the steel strip to a diffusion treatment in a non-oxidizing gas atmosphere not containing SiCl4 to diffuse Si approximately uniformly inside the steel strip, and then cooling and winding up the strip. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 62-227078 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a substrate processing method and a substrate processing apparatus capable of improving the processability of a photoresist film in EUV exposure. [Means for solving the problem]

[0005] A substrate processing method according to an embodiment of the present disclosure includes steps a) and b). In step a), a substrate having a photoresist film containing a metal oxide formed on its surface is placed in a chamber. In step b), a gas containing silicon is supplied into the chamber to replace a metal constituting the metal oxide contained in the photoresist film with silicon. Effect of the Invention

[0006] According to the present disclosure, it is possible to improve the processability of a photoresist film in EUV exposure. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a diagram showing the EUV absorption cross section of an atom. [Diagram 2] FIG. 2 is a diagram illustrating an example of a substrate according to an embodiment. [Diagram 3] FIG. 3 is a diagram illustrating an example of a flow of substrate processing for forming a pattern on a substrate. [Figure 4] FIG. 4 is a diagram showing an example of a replacement state of a metal oxide resist film on a substrate according to the embodiment. [Diagram 5] FIG. 5 is a diagram showing an example of a schematic configuration of a substrate processing apparatus according to an embodiment. [Figure 6] FIG. 6 is a diagram showing an example of a flow of substrate processing according to the embodiment. [Figure 7] FIG. 7 is a diagram illustrating an example of a flow of substrate processing for performing double patterning on a substrate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the substrate processing method and substrate processing apparatus disclosed in the present application will be described in detail with reference to the accompanying drawings. Note that the substrate processing method and substrate processing apparatus disclosed in the present application are not limited to the preferred embodiments.

[0009] In the manufacture of semiconductor devices, a pattern is formed on a substrate such as a semiconductor wafer by a lithography process. In the lithography process, a photoresist film is formed on the surface of the substrate. In the lithography process, the formed photoresist film is selectively exposed through a mask having a predetermined pattern formed thereon, and a development process is performed to form a pattern of a predetermined shape in the photoresist film. Conventionally, a carbon-based photoresist has been used for the photoresist film. For example, a chemically amplified resist has been used for the photoresist film.

[0010] In recent years, along with the miniaturization of semiconductor devices, miniaturization is also progressing in lithography technology. One method of miniaturization is shortening the wavelength of the exposure light source. In recent years, EUV exposure using EUV (Extreme Ultra Violet) light has been considered.

[0011] However, conventional carbon-based photoresist films have poor absorption of EUV light and take a long time to react. Therefore, photoresist films containing metal oxides are used for EUV exposure. For example, metal oxide resists (MOR) such as tin oxide are used for the photoresist film for EUV exposure.

[0012] FIG. 1 is a diagram showing the EUV absorption cross section of an atom. The horizontal axis of FIG. 1 is the atomic number of each atom. The horizontal axis of FIG. 1 is the atomic absorption cross section of the atom. The absorption cross section indicates the proportion of EUV that is absorbed when passing through an atom. FIG. 1 shows the absorption cross section of each atom with each atomic number. For example, the absorption cross section of atomic number 12 is the absorption cross section of carbon. The absorption cross section of atomic number 50 is the absorption cross section of tin. Tin has a larger EUV absorption cross section than carbon. In other words, tin has a higher absorption rate of EUV than carbon.

[0013] However, metal oxide resists have poor processability compared to conventional carbon-based photoresists, so the present disclosure provides techniques to improve the processability of photoresist films in EUV exposure.

[0014] (Embodiment) An embodiment will be described. First, an example of a substrate 10 used in the substrate processing according to the embodiment will be described. FIG. 2 is a diagram for explaining an example of the substrate 10 according to the embodiment. FIG. 2 shows the substrate 10. The substrate 10 has a first lower layer film 12 and a second lower layer film 13 laminated in this order on a silicon substrate 11. The first lower layer film 12 is, for example, SiC(H), SiOC(H), SiOCN, SiOx , SiN x The second underlayer film 13 is, for example, SiC(H), SiOC(H), SiOCN, SiO x , SiN x , DLC (Diamond-Like Carbon), aC (Amorphous Carbon), or SOG. Note that the configuration of the substrate 10 shown in Fig. 2 is an example, and is not limited thereto. Films necessary for manufacturing a semiconductor device are formed on the substrate 10 as necessary.

[0015] When manufacturing a semiconductor device, a pattern is formed on the substrate 10 by a lithography process. In the lithography process, a photoresist film containing a metal oxide is formed on the surface of the substrate 10. The metal oxide is any oxide of Sn (tin), W (tungsten), Te (tellurium), Sb (antimony), In (indium), Zn (zinc), Zr (zirconium), In (indium), or Hf (hafnium). For example, in EUV exposure, a metal oxide resist film 20 is formed as a photoresist film on the surface of the substrate 10. For example, a tin oxide film is formed as the metal oxide resist film 20 on the substrate 10.

[0016] Here, an example of the flow of substrate processing for forming a pattern on the substrate 10 according to the embodiment will be described. Fig. 3 is a diagram illustrating an example of the flow of substrate processing for forming a pattern on the substrate 10. A metal oxide resist film 20 is formed on the surface of the substrate 10.

[0017] When a pattern is formed in the metal oxide resist film 20 of the substrate 10, EUV exposure is performed. In the EUV exposure, the metal oxide resist film 20 of the substrate 10 is irradiated with EUV light through a mask 30 on which a predetermined pattern is formed. In the metal oxide resist film 20, an exposed portion 20a exposed to EUV light and an unexposed portion 20b not exposed to EUV light are formed corresponding to the mask 30. Next, a post exposure bake (PEB) is performed. In the post exposure bake, the substrate 10 that has been subjected to EUV exposure is heated to promote a reaction of the exposed portion 20a of the metal oxide resist film 20. Next, the substrate 10 is developed. For example, in the metal oxide resist film 20, a difference occurs in the etching rate between the exposed portion 20a and the unexposed portion 20b. The metal oxide resist film 20 is etched using the selectivity between the exposed portion 20a and the unexposed portion 20b, thereby developing the substrate 10. For example, the metal oxide resist film 20 is etched using tin oxide (SnO x ) film, the exposed portion 20a of the metal oxide resist film 20 changes to SnO2 by EUV exposure. x Since an etching selectivity can be obtained, negative-tone patterning is possible, which removes the unexposed portion 20b by etching and leaves the exposed portion 20a. Figure 3 shows the case where negative-tone development is performed, which leaves the exposed portion 20a of the metal oxide resist film 20.

[0018] However, the metal oxide resist film 20 has poor processability compared to carbon-based resists. For example, the metal oxide resist film 20 is prone to generating residues, which are difficult to remove. For example, the metal oxide resist film 20 leaves SnO residues. If residues remain on the metal oxide resist film 20, the residues are transferred when the pattern is transferred to the substrate 10, resulting in a decrease in pattern fidelity and an increase in roughness. In addition, gases such as HBr and BCl3, which are difficult to handle, are required to etch SnO.

[0019] Therefore, in the substrate processing according to the embodiment, the substrate 10 is exposed to a gas containing silicon. For example, the substrate 10 is placed in a chamber. Then, a gas containing silicon is supplied into the chamber, and the substrate 10 is exposed to the gas containing silicon. The gas containing silicon includes silicon halides and hydrides. The silicon halides and hydrides are preferably those which form silicon oxides selected from SiCl4 (tetrachlorosilane), SiH2Cl2 (dichlorosilane), SiF4 (tetrafluorosilane), SiH4 (monosilane), Si2H6 (disilane), and Si2Cl6 (hexachlorodisilane). Examples of silicon halides include SiH2Cl2, Si2Cl6, SiCl4, and SiF4. Examples of hydrides include SiH4 and Si2H6. For example, the pressure in the chamber is set to 1 Torr (133.32 Pa), the temperature of the substrate 10 is set to 200° C., and the substrate 10 is exposed to SiH2Cl2 for 20 minutes. When the metal oxide resist film 20 on the substrate 10 is exposed to a gas containing silicon, the metal constituting the metal oxide contained in the metal oxide resist film 20 is replaced with silicon. Furthermore, a metal compound is generated as a by-product by the replacement. The by-product metal compound is vaporized and removed. For example, if the metal oxide resist film 20 is made of SnO x In this case, SnO2 in the exposed portion 20a is replaced by SiO2. Furthermore, SnCl4 is generated as a by-product by the replacement. The SnCl4 is vaporized and removed from the metal oxide resist film 20.

[0020] In this way, the SnO2 in the exposed portion 20a of the metal oxide resist film 20 is replaced by SiO2, so that the exposed portion 20a can be processed using a conventional SiO2 processing technique. Furthermore, since SnO such as residues is also replaced by SiO2, it can be removed using a conventional SiO2 processing technique. In this way, the substrate processing according to the embodiment can improve the processability of the metal oxide resist film 20 used as a photoresist film in EUV exposure.

[0021] Here, the mechanism by which the substitution occurs will be assumed. In the following, an example will be described in which SnO2 in the exposed portion 20a of the metal oxide resist film 20 reacts with SiCl4, which is formed from silicon halides and hydrides contained in a silicon-containing gas, as shown in the following reaction formula (1).

[0022] SiCl4+SnO2→SiO2+SnCl4(1)

[0023] The Gibbs free energy before the reaction in reaction equation (1) can be expressed as (2) below. The Gibbs free energy after the reaction in reaction equation (1) can be expressed as (3) below.

[0024] Before reaction SiCl4(g):-657.01[kJ / mol]+SnO2(c):-515.74[kJ / mol] (2) After reaction SiO2(c):-855[kJ / mol]+SnCl4:-440.2[kJ / mol] (3)

[0025] The total Gibbs free energy is more favorable after the reaction than before the reaction, so it is speculated that the substitution in reaction (1) occurs.

[0026] In addition, SnO2 has a much higher vapor pressure than SiO2. From this point of view, it is assumed that the substitution shown in reaction formula (1) occurs. In addition, since tin (Sn) and silicon (Si) are both in group 14, it is assumed that substitution occurs easily.

[0027] The rate at which SnO2 in the exposed portion 20a of the metal oxide resist film 20 is replaced by SiO2 varies depending on the temperature of the substrate 10. FIG. 4 is a diagram showing an example of the replacement state of the metal oxide resist film 20 of the substrate 10 according to the embodiment. FIG. 4(A) shows a HAADF-STEM (High-Angle Annular Dark Field Scanning Transmission Electron Microscopy) image of the substrate 10 when the temperature of the substrate 10 is a low temperature of 150°C or less, an image showing the distribution of Sn, and an image showing the distribution of Si. FIG. 4(B) shows a HAADF-STEM image of the substrate 10 when the temperature of the substrate 10 is a high temperature of 150°C or more, an image showing the distribution of Sn, and an image showing the distribution of Si. As shown in FIG. 4(B), at high temperatures, Sn is not distributed, but Si is distributed, so SnO2 is replaced by SiO2, and the replacement rate is fast. On the other hand, as shown in FIG. 4(A), at low temperatures, Sn and Si are distributed together, so the replacement rate is slow.

[0028] For example, when the substrate 10 is exposed to dichlorosilane gas at 5 Torr (666.61 Pa) at temperatures of 50°C, 100°C, 150°C, and 200°C, the rate at which SnO2 in the exposed portion 20a of the metal oxide resist film 20 is replaced by SiO2 is as follows:

[0029] 50℃: 0.15[nm / min] 100℃: 0.45[nm / min] 150℃: 0.62[nm / min] 200℃:>0.62[nm / min]

[0030] When the temperature of the substrate 10 was raised to 200° C., the exposed portion 20a was completely replaced. Therefore, the replacement rate at 200° C. is shown as being greater than 0.62 [nm / min].

[0031] The substitution occurs by gradually penetrating from the surface of the metal oxide resist film 20 to the inside. The lower the temperature of the substrate 10, the slower the substitution speed, and the longer it takes to substitute the entire exposed portion 20a. The temperature of the substrate 10 during the substitution may be 50°C or higher. On the other hand, if the temperature of the substrate 10 is too high, the substrate 10 may be damaged by heat. The upper limit of the temperature of the substrate 10 is preferably set to a temperature at which the substrate 10 is not damaged by heat. For example, the temperature of the substrate 10 during the substitution is preferably in the range of 50 to 500°C. To rapidly proceed with the substitution, the temperature of the substrate 10 is preferably 100°C or higher, and more preferably 200°C or higher.

[0032] (Device configuration) Next, a description will be given of an example of the configuration of the substrate processing apparatus 100 according to an embodiment. Fig. 5 is a diagram showing an example of a schematic configuration of the substrate processing apparatus 100 according to an embodiment.

[0033] The substrate processing apparatus 100 includes a chamber 110, a gas supply unit 120, a stage 130, and an exhaust unit 140. The substrate processing apparatus 100 also includes a gas inlet unit. The chamber 110 is configured to be airtight. The gas inlet unit is configured to introduce at least one process gas into the chamber 110. The gas inlet unit includes a showerhead 113. The stage 130 is disposed within the chamber 110. The showerhead 113 is disposed above the stage 130. In one embodiment, the showerhead 113 forms at least a portion of a ceiling of the chamber 110.

[0034] The stage 130 has a mounting surface 130a formed on its upper surface for supporting the substrate 10. The mounting surface 130a is formed to be wider than the substrate 10. The chamber 110 is provided with a loading / unloading port (not shown). The loading / unloading port can be opened and closed by a gate valve. When the substrate 10 is loaded into the substrate processing apparatus 100, the loading / unloading port (not shown) provided in the chamber 110 is opened. The substrate 10 is loaded into the chamber 110 from the loading / unloading port by a transfer mechanism such as a transfer arm, and placed on the mounting surface 130a of the stage 130.

[0035] The stage 130 has a heater 131 provided therein. A power supply 132 is connected to the heater 131. The power supply 132 supplies power to the heater 131. The heater 131 generates heat by the power supplied from the power supply 132. The power supply 132 is capable of controlling the power supplied to the heater 131. The substrate processing apparatus 100 is configured to be capable of controlling the temperature of the substrate 10 by controlling the power supplied from the power supply 132 to the heater 131 to control the temperature of the heater 131.

[0036] The shower head 113 is configured to introduce at least one process gas from the gas supply unit 120 into the chamber 110. The shower head 113 has at least one gas supply port 113a, at least one gas diffusion chamber 113b, and multiple gas inlets 113c. The process gas supplied to the gas supply port 113a passes through the gas diffusion chamber 113b and is introduced into the chamber 110 from the multiple gas inlets 113c.

[0037] The gas supply unit 120 includes at least one gas source 121 and at least one flow rate controller 122. Each flow rate controller 122 may include, for example, a mass flow controller or a pressure-controlled flow rate controller. The gas supply unit 120 supplies a silicon-containing gas from the gas source 121 to the shower head 113 via the flow rate controller 122.

[0038] The exhaust unit 140 is connected to, for example, a gas exhaust port 110a provided at the bottom of the chamber 110. The exhaust unit 140 may include a pressure regulating valve and a vacuum pump. The pressure inside the chamber 110 is adjusted by the pressure regulating valve. The vacuum pump may include a turbo molecular pump, a dry pump, or a combination thereof.

[0039] The substrate processing apparatus 100 includes a control unit 150. The control unit 150 controls each unit of the substrate processing apparatus 100 and causes the substrate processing apparatus 100 to perform substrate processing.

[0040] (Substrate processing) Next, an example of substrate processing including the substrate processing method of the present disclosure will be described. Fig. 6 is a diagram showing an example of a substrate processing flow according to an embodiment. Fig. 6 shows a substrate processing flow for forming a pattern on the substrate 10 shown in Fig. 3.

[0041] A photoresist film containing a metal oxide is formed on the surface of the substrate 10 (step S10). For example, the substrate 10 is transported to a film forming apparatus, and a metal oxide resist film 20 such as a tin oxide film is formed on the substrate 10 in the film forming apparatus. The metal oxide resist film 20 may be formed on the substrate 10 by spin coating or by vacuum film forming.

[0042] Next, the substrate 10 on which the photoresist film containing metal oxide has been formed is subjected to EUV exposure (step S11). For example, the substrate 10 is transported to an EUV exposure apparatus, and the substrate 10 is subjected to EUV exposure in the EUV exposure apparatus. In the EUV exposure, the metal oxide resist film 20 on the substrate 10 is irradiated with EUV light through a mask 30 on which a predetermined pattern has been formed.

[0043] Next, post-exposure bake (PEB) is performed on the EUV-exposed substrate 10 (step S12). For example, the substrate 10 is transferred to a heat treatment device, and post-exposure bake is performed on the substrate 10 in the heat treatment device.

[0044] Next, the substrate 10 that has been subjected to the post-exposure bake is developed (step S13). For example, the substrate 10 is transported to an etching device, and the metal oxide resist film 20 of the substrate 10 is etched by the etching device, thereby developing the pattern formed in the metal oxide resist film 20.

[0045] Next, the developed substrate 10 is exposed to a gas containing silicon (step S14). For example, the substrate 10 is transported to the substrate processing apparatus 100 and placed on the stage 130. The substrate processing apparatus 100 reduces the pressure in the chamber 110 to a predetermined pressure suitable for exposure to the gas containing silicon by the exhaust unit 140. The substrate processing apparatus 100 also controls the temperature of the heater 131 to control the temperature of the substrate 10 placed on the stage 130 to a range of 50 to 500°C. The substrate processing apparatus 100 then supplies a gas containing silicon from the gas supply unit 120 into the chamber 110 to expose the substrate 10 to the gas containing silicon. For example, the substrate processing apparatus 100 sets the pressure in the chamber 110 to 1 Torr (133.32 Pa), sets the temperature of the substrate 10 to 200°C, and exposes the substrate 10 to SiH2Cl2 gas for 20 minutes. As a result, the metal constituting the metal oxide contained in the developed metal oxide resist film 20 is replaced with silicon. For example, the metal oxide resist film 20 is made of SnO x If so, it will be replaced by SiO2.

[0046] This allows the exposed portion 20a to be processed using a conventional SiO2 processing technique. In this manner, the substrate processing according to the embodiment can improve the processability of the metal oxide resist film 20 used as a photoresist film in EUV exposure.

[0047] Next, an example of processing the substrate 10 on which a pattern is formed will be described. In the following, as an example of processing the substrate 10, a flow of substrate processing for performing double patterning on the substrate 10 will be described. FIG. 7 is a diagram for explaining an example of a flow of substrate processing for performing double patterning on the substrate 10. In the metal oxide resist film 20 of the substrate 10, a pattern is formed by the exposed portion 20a by, for example, the substrate processing shown in FIG. 3. The SnO2 in the exposed portion 20a is replaced with SiO2.

[0048] When double patterning of the substrate 10 is performed, for example, a SiN xA SiN film 25 is formed on the substrate 10 so as to cover the unevenness caused by the exposed portion 20a of the metal oxide resist film 20. x Next, the SiN film 25 formed on the substrate 10 is removed by plasma etching or the like. x Anisotropic etching of the film 25 is performed. SiN x By performing anisotropic etching of the film 25, the SiN x The film 25 is etched. x By performing anisotropic etching of the film 25, the SiN x The film 25 remains. Next, the SiO 2 is removed from the substrate 10 by plasma etching or the like. x Anisotropic etching is performed on SiO x By performing the anisotropic etching, the exposed portion 20a of the substrate 10 is etched from the upper surface side, and the SiN x In the double patterning of the substrate 10, the remaining SiN x The film 25 is used as a mask to pattern the substrate 10. This allows fine processing of the substrate 10 to be achieved.

[0049] In this manner, by the substrate processing method according to the embodiment, SnO2 in the exposed portion 20a of the metal oxide resist film 20 is replaced with SiO2, and thus double patterning of the substrate 10 can be realized.

[0050] In the above-described embodiment, the metal oxide resist film 20 is mainly described as a tin oxide film. However, the disclosed technology is not limited to this. It is presumed that the substitution shown in the embodiment occurs if the element has catenation properties. Catenation means that atoms of the same element are bonded in a long chain shape. For example, the metal oxide resist film 20 may be a film of any oxide of W, Te, Sb, In, Zn, Zr, or Hf. In this case, too, the oxide of W, Te, Sb, In, Zn, Zr, or Hf contained in the metal oxide resist film 20 can be replaced with silicon by the substrate processing method according to the embodiment. This can improve the processability of the photoresist film in EUV exposure.

[0051] In the above embodiment, the substrate processing apparatus 100 is described as being configured to expose the substrates 10 one by one to a gas containing silicon. However, the disclosed technology is not limited to this. The substrate processing apparatus 100 may be configured to be capable of arranging a plurality of substrates 10 inside the chamber 110, and may be configured to expose a plurality of substrates 10 to a gas containing silicon.

[0052] The embodiment has been described above. As described above, the substrate processing method according to the embodiment includes a step a) (e.g., step S14) and a step b) (e.g., step S14). In the step a, the substrate 10 having a photoresist film containing a metal oxide formed on its surface is placed in the chamber 110. In the step b), a gas containing silicon is supplied into the chamber 110 to replace the metal constituting the metal oxide contained in the photoresist film with silicon. As a result, the substrate processing method according to the embodiment can improve the processability of the photoresist film in EUV exposure.

[0053] Moreover, the photoresist film is a metal oxide resist film 20. The substrate processing method according to the embodiment further includes a step c) prior to the step a) and the step b). In the step c), the metal oxide resist film 20 formed on the surface of the substrate 10 is exposed to EUV light. Thereby, the substrate processing method according to the embodiment can improve the processability of the metal oxide resist film 20 in EUV exposure.

[0054] Moreover, the substrate processing method according to the embodiment further includes a step d) after the step c) and before the step b). The step d) is after the step c) and before the step b), and develops the metal oxide resist film 20 exposed to EUV. Thus, the substrate processing method according to the embodiment can improve the processability of the developed metal oxide resist film 20.

[0055] The metal oxide is an oxide of any one of Sn, W, Te, Sb, In, Zn, Zr, and Hf. Thereby, the substrate processing method according to the embodiment can replace the metal constituting the metal oxide with silicon.

[0056] The metal oxide resist film 20 is a tin oxide film. Thus, in the substrate processing method according to the embodiment, tin constituting the tin oxide film can be replaced with silicon.

[0057] The gas contains a silicon halide and a hydride. In step b), the metal oxide contained in the developed metal oxide resist film 20 is brought into contact with the silicon halide and the hydride, and the metal constituting the metal oxide is replaced with silicon. In this way, the substrate processing method according to the embodiment can replace the metal constituting the metal oxide with silicon.

[0058] In addition, the silicon halide and the hydride form a silicon oxide selected from the group consisting of SiCl4, SiH2Cl2, SiF4, SiH4, Si2H6, and Si2Cl6. As a result, the substrate processing method according to the embodiment can replace the metal constituting the metal oxide with silicon.

[0059] In step b), the substrate 10 is heated to 50° C. or higher, and a gas is supplied into the chamber 110 to replace the metal constituting the metal oxide contained in the photoresist film with silicon. In this way, the substrate processing method according to the embodiment can replace the metal constituting the metal oxide with silicon.

[0060] Moreover, the substrate processing method according to the embodiment further includes a step e) after the step b). The step e) is a double patterning of the photoresist film. Thereby, the substrate processing method according to the embodiment can form a fine pattern in the photoresist film.

[0061] Moreover, the substrate processing apparatus 100 according to the embodiment includes a chamber 110, a stage 130, and a gas supply unit 120. The stage 130 is disposed in the chamber 110, and a substrate 10 having a photoresist film containing a metal oxide formed on its surface is placed on the stage 130. The gas supply unit 120 supplies a gas containing silicon into the chamber 110. As a result, the substrate processing apparatus 100 according to the embodiment can improve the processability of the photoresist film in EUV exposure.

[0062] (others) It should be noted that the technology disclosed in the present application is not limited to the above-described embodiment, and various modifications are possible within the scope of the gist thereof.

[0063] It should be noted that the embodiments disclosed herein are illustrative in all respects and should not be construed as limiting. Indeed, the above-described embodiments may be embodied in various forms. Furthermore, the above-described embodiments may be omitted, substituted, or modified in various forms without departing from the scope and spirit of the appended claims.

[0064] In addition, the following supplementary notes are disclosed regarding the above embodiment.

[0065] (Appendix 1) a) placing a substrate having a photoresist film containing a metal oxide formed on a surface thereof in a chamber; b) supplying a silicon-containing gas into the chamber to replace metals constituting metal oxides contained in the photoresist film with silicon; A substrate processing method comprising:

[0066] (Appendix 2) the photoresist film is a metal oxide resist film, c) exposing the metal oxide resist film formed on the surface of the substrate to EUV (Extreme Ultra Violet) prior to the steps a) and b). 2. The substrate processing method of claim 1, further comprising:

[0067] (Appendix 3) d) developing the EUV-exposed metal oxide resist film after the step c) and before the step b). 3. The substrate processing method according to claim 2, further comprising:

[0068] (Appendix 4) The metal oxide is an oxide of any one of Sn, W, Te, Sb, In, Zn, Zr, and Hf. 4. A substrate processing method according to any one of claims 1 to 3.

[0069] (Appendix 5) The metal oxide resist film is a tin oxide film. 4. The substrate processing method according to claim 2 or 3.

[0070] (Appendix 6) the gas comprises a silicon halide and a silicon hydride; The step b) includes contacting a metal oxide contained in the developed metal oxide resist film with a silicon halide and a silicon hydride to substitute the metal constituting the metal oxide with silicon. 4. The substrate processing method of claim 3.

[0071] (Appendix 7) The silicon halide and the hydride form a silicon oxide selected from SiCl4, SiH2Cl2, SiF4, SiH4, Si2H6, and Si2Cl6. 7. The substrate processing method according to claim 6.

[0072] (Appendix 8) The step b) heats the substrate to 50° C. or higher, supplies the gas into the chamber, and replaces metals constituting metal oxides contained in the photoresist film with silicon. 8. A substrate processing method according to any one of claims 1 to 7.

[0073] (Appendix 9) e) performing double patterning of the photoresist film after the step b). 9. A substrate processing method according to any one of claims 1 to 8.

[0074] (Appendix 10) A chamber; a stage disposed within the chamber, on which a substrate having a photoresist film containing a metal oxide formed on its surface is placed; a gas supply unit for supplying a silicon-containing gas into the chamber; A substrate processing apparatus comprising: [Explanation of symbols]

[0075] 10 Substrate 11 Silicon substrate 12 1st lower layer film 13 Second lower layer film 20 Metal oxide resist film 20a Exposed area 20b Unexposed area 25SiN x film 30 Mask 100 Substrate processing apparatus 110 Chamber 120 Gas supply section 130 Stages 130a Placement surface 131 Heater 132 Power supply 140 Exhaust section 150 Control section

Claims

1. a) placing a substrate having a photoresist film containing a metal oxide formed on a surface thereof in a chamber; b) supplying a silicon-containing gas into the chamber to replace metals constituting metal oxides contained in the photoresist film with silicon; A substrate processing method comprising:

2. the photoresist film is a metal oxide resist film, c) exposing the metal oxide resist film formed on the surface of the substrate to EUV (Extreme Ultra Violet) prior to the steps a) and b). The method of claim 1 further comprising:

3. d) developing the EUV-exposed metal oxide resist film after the step c) and before the step b). The method of claim 2 further comprising:

4. The metal oxide is an oxide of any one of Sn, W, Te, Sb, In, Zn, Zr, and Hf. The method of claim 1 .

5. The metal oxide resist film is a tin oxide film. The substrate processing method according to claim 2 .

6. the gas comprises a silicon halide and a silicon hydride; The step b) comprises contacting a metal oxide contained in the developed metal oxide resist film with a silicon halide and a silicon hydride to substitute a metal constituting the metal oxide with silicon. The substrate processing method according to claim 3 .

7. The silicon halide and the hydride are SiCl ４ , SiH ２ C ２ , SiF ４ , SiH ４ , Si ２ H ６ , Si ２ C ６ forming a silicon oxide selected from The substrate processing method according to claim 6 .

8. The step b) includes heating the substrate to 50° C. or higher and supplying the gas into the chamber to replace metals constituting metal oxides contained in the photoresist film with silicon. The method of claim 1 .

9. e) performing double patterning of the photoresist film after the step b); The method of claim 1 further comprising:

10. A chamber; a stage disposed within the chamber, on which a substrate having a photoresist film containing a metal oxide formed on its surface is placed; a gas supply unit for supplying a silicon-containing gas into the chamber; A substrate processing apparatus comprising:

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