Substrate processing method and substrate processing apparatus

Abstract

The substrate processing method includes a step (a) and a step (b). In the step (a), a substrate, on the surface of which a photoresist film is formed, is disposed in a chamber, and the photoresist film contains a metal oxide. In the step (b), a gas containing silicon is supplied into the chamber, and the metal constituting the metal oxide contained in the photoresist film is replaced with silicon.

Description

Technical Field

[0001] Various aspects and embodiments of this disclosure relate to a substrate processing method and a substrate processing apparatus. Background Technology

[0002] Patent Document 1 discloses a method for manufacturing high-silicon steel strip in a continuous production line, characterized in that the steel strip is continuously subjected to silicon diffusion treatment by chemical vapor deposition at a temperature of 1023°C to 1200°C in a non-oxidizing gas atmosphere containing SiCl4 at a mol fraction of 5% to 35%, followed by a diffusion treatment in a non-oxidizing gas atmosphere not containing SiCl4 to allow Si to diffuse substantially uniformly into the interior of the steel strip, and then wound up after cooling.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 62-227078 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] This disclosure provides a substrate processing method and a substrate processing apparatus that can improve the processability of photoresist films during EUV exposure.

[0008] Solution for solving the problem

[0009] One aspect of the substrate processing method disclosed herein includes steps (a) and (b). In step (a), a substrate having a photoresist film formed on its surface is disposed in a chamber, the photoresist film being a photoresist film comprising a metal oxide. In step (b), a silicon-containing gas is supplied into the chamber to replace the metal in the metal oxide comprising the photoresist film with silicon.

[0010] Invention Effects

[0011] According to this disclosure, the processability of photoresist films in EUV exposure can be improved. Attached Figure Description

[0012] Figure 1 This is a diagram showing the absorption cross section of an atom using EUV.

[0013] Figure 2 This is a diagram illustrating an example of the substrate involved in the embodiment.

[0014] Figure 3 This is a diagram illustrating an example of a substrate processing flow for forming patterns on a substrate.

[0015] Figure 4 This is a diagram illustrating an example of the displacement status of the metal oxide resist film on the substrate involved in the embodiment.

[0016] Figure 5 This is a diagram illustrating an example of the general structure of the substrate processing apparatus according to the embodiment.

[0017] Figure 6 This is a diagram illustrating an example of the substrate processing flow involved in the embodiment.

[0018] Figure 7 This diagram illustrates an example of a substrate processing flow for performing double patterning on a substrate. Detailed Implementation

[0019] Hereinafter, embodiments of the substrate processing method and substrate processing apparatus disclosed in this application will be described in detail with reference to the accompanying drawings. However, the disclosed substrate processing method and substrate processing apparatus are not intended to be limited by these embodiments.

[0020] In the manufacture of semiconductor devices, patterns are formed on substrates such as semiconductor wafers using a photolithography process. In the photolithography process, a photoresist film is formed on the surface of the substrate. Then, in the photolithography process, the formed photoresist film is selectively exposed through a mask with a predetermined pattern, and a development process is performed, thereby forming a pattern of a predetermined shape on the photoresist film. Conventionally, carbon-based photoresists are used. For example, conventionally, chemically amplified photoresists are used.

[0021] In recent years, with the miniaturization of semiconductor devices, miniaturization in photolithography technology is also progressing. One method of miniaturization is shortening the wavelength of the exposure light source. Recently, research has focused on EUV (Extreme Ultraviolet) exposure.

[0022] Furthermore, conventional carbon-based photoresist films exhibit poor EUV absorption and require a long reaction time. Therefore, photoresist films containing metal oxides are used in EUV exposure. For example, metal oxide resists (MOR) such as tin oxide are used in EUV exposure.

[0023] Figure 1 This is a diagram showing the absorption cross section of an atom using EUV. Figure 1 The horizontal axis represents the atomic number of each atom. Figure 1The horizontal axis represents the atomic absorption cross section. The absorption cross section indicates the proportion of EUV absorbed as it passes through atoms. Figure 1 The diagram shows the absorption cross-sections of atoms with different atomic numbers. For example, the absorption cross-section for atomic number 12 is the same as that for carbon. The absorption cross-section for atomic number 50 is the same as that for tin. Tin has a larger EUV absorption cross-section than carbon. That is, tin has a higher EUV absorption rate than carbon.

[0024] However, metal oxide photoresists have poor processability compared to conventional carbon-based photoresists. Therefore, this disclosure provides a technique for improving the processability of photoresist films during EUV exposure.

[0025] (Implementation Method)

[0026] The implementation method will be described. First, an example of the substrate 10 used in the substrate processing involved in the implementation method will be described. Figure 2 This is a diagram illustrating an example of the substrate 10 involved in the embodiment. Figure 2 The image shows a substrate 10. A first lower layer film 12 and a second lower layer film 13 are sequentially stacked on a silicon substrate 11. The first lower layer film 12 is, for example, SiC(H), SiOC(H), SiOCN, or SiO. x SiN x The second lower layer film 13 is, for example, SiC(H), SiOC(H), SiOCN, or SiO. x SiN x Any one of DLC (diamond-like carbon), aC (amorphous carbon), and SOG. In addition, Figure 2 The structure of the substrate 10 shown is an example and is not limited thereto. Films required for the manufacture of semiconductor devices may be formed on the substrate 10 as needed.

[0027] In the manufacture of a semiconductor device, a pattern is formed on a substrate 10 through a photolithography process. During the photolithography process, a photoresist film comprising a metal oxide is formed on the surface of the substrate 10. The metal oxide is an oxide of any one of Sn (tin), W (tungsten), Te (tellurium), Sb (antimony), In (indium), Zn (zinc), Zr (zirconium), In (indium), and Hf (hafnium). For example, in EUV exposure, a metal oxide photoresist film 20 is formed on the surface of the substrate 10 as a photoresist film. For example, a tin oxide film is formed on the substrate 10 as the metal oxide photoresist film 20.

[0028] Here, an example of the substrate processing flow for forming patterns on the substrate 10 according to the embodiment will be described. Figure 3 This diagram illustrates an example of a substrate processing flow for forming a pattern on substrate 10. A metal oxide resist film 20 is formed on the surface of substrate 10.

[0029] When a pattern is formed on the metal oxide resist film 20 of the substrate 10, EUV exposure is performed. During EUV exposure, EUV light is irradiated onto the metal oxide resist film 20 of the substrate 10 via a mask 30 with a predetermined pattern. On the metal oxide resist film 20, exposed portions 20a and unexposed portions 20b are formed corresponding to the mask 30, respectively. Next, post-exposure baking (PEB) is performed. During PEB, the substrate 10 after EUV exposure is heated to promote the reaction of the exposed portions 20a of the metal oxide resist film 20. Next, development of the substrate 10 is performed. For example, a difference in etching rate exists between the exposed portions 20a and the unexposed portions 20b of the metal oxide resist film 20. The substrate 10 is developed by etching the metal oxide resist film 20 using the selectivity ratio between the exposed portions 20a and the unexposed portions 20b. For example, when the metal oxide resist film 20 is set as tin oxide (SnO) x In the case of a film, by EUV exposure, the exposed portion 20a of the metal oxide resist film 20 changes to SnO2. The SnO2 in the exposed portion 20a differs from the SnO2 in the unexposed portion 20b. x An etch selectivity ratio can be achieved, thus enabling the patterning of a negative tone that preserves the exposed portion 20a by etching away the unexposed portion 20b. Figure 3 This illustrates a case where negative development is performed, preserving the exposed portion 20a of the metal oxide resist film 20.

[0030] Furthermore, the metal oxide resist film 20 has poorer processability compared to carbon-based resists. For example, the metal oxide resist film 20 is prone to residue formation, and this residue is difficult to remove. For instance, SnO residue may remain in the metal oxide resist film 20. If residue remains in the metal oxide resist film 20, the areas where the residue will be transferred during pattern transfer to the substrate 10 will suffer from reduced pattern fidelity and poor surface roughness. In addition, SnO etching requires gases such as HBr and BCl3, which are difficult to handle.

[0031] Therefore, in the substrate processing according to the embodiment, the substrate 10 is exposed to a silicon-containing gas. For example, the substrate 10 is disposed in a chamber. Then, a silicon-containing gas is supplied to the chamber, exposing the substrate 10 to the silicon-containing gas. The silicon-containing gas includes silicon halides and hydrides. The silicon halides and hydrides are preferably selected from SiCl4 (tetrachlorosilane), SiH2Cl2 (dichlorosilane), SiF4 (tetrafluorosilane), SiH4 (methylsilane), Si2H6 (dichlorosilane), and Si2Cl6 (hexachlorodisilane) to form silicon oxide. 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), and the temperature of the substrate 10 is set to 200°C, then the substrate 10 is exposed to SiH2Cl2 for 20 minutes. When the metal oxide resist film 20 of the substrate 10 is exposed to a silicon-containing gas, the metal of the metal oxide contained in the metal oxide resist film 20 is replaced with silicon. Furthermore, a metal compound is generated as a byproduct due to the replacement. The metal compound, as a byproduct, is vaporized and removed. For example, when the metal oxide resist film 20 is SnO… x In this case, SnO2 in the exposed portion 20a is replaced with SiO2. Additionally, SnCl4 is generated as a byproduct due to the replacement. SnCl4 vaporizes and is removed from the metal oxide resist film 20.

[0032] By replacing SnO2 with SiO2 in the exposed portion 20a of the metal oxide resist film 20, the exposed portion 20a can be processed using conventional SiO2 processing techniques. Furthermore, SnO residues are also replaced with SiO2, thus allowing them to be removed using conventional SiO2 processing techniques. In this way, the substrate processing according to this embodiment improves the processability of the metal oxide resist film 20 used as a photoresist film in EUV exposure.

[0033] Here, we speculate on the mechanism of the substitution. Hereinafter, we will take the case where SnO2 in the exposed portion 20a of the metal oxide resist film 20 undergoes the reaction as shown in the following reaction formula (1) by SiCl4 formed by silicon halides and hydrides contained in a silicon-containing gas.

[0034] SiCl4+SnO2→SiO2+SnCl4 (1)

[0035] The Gibbs free energy of reaction (1) before the reaction is expressed as (2). In addition, the Gibbs free energy of reaction (1) after the reaction is expressed as (3).

[0036] Before the reaction

[0037] SiCl4 (g): -657.01 [kJ / mol] + SnO2 (c): -515.74 [kJ / mol] (2)

[0038] After the reaction

[0039] SiO2 (c): -855[kJ / mol]+SnCl4: -440.2[kJ / mol] (3)

[0040] The total Gibbs free energy is predominant after the reaction compared to before the reaction. Therefore, it is speculated that the substitution reaction (1) occurs.

[0041] Furthermore, the vapor pressure of SnO2 is significantly greater than that of SiO2. Based on this, it is also speculated that the substitution reaction (1) occurs. In addition, both tin (Sn) and silicon (Si) are group 14, so it is speculated that substitution is likely to occur.

[0042] The rate at which SnO2 is replaced by SiO2 in the exposed portion 20a of the metal oxide resist film 20 varies depending on the temperature of the substrate 10. Figure 4 This is a diagram illustrating an example of the replacement state of the metal oxide resist film 20 on the substrate 10 according to the embodiment. Figure 4 (A) shows HAADF-STEM (High-Angle Annular Dark Field Scanning Transmission Electron Microscopy) images of substrate 10 when the temperature of substrate 10 is set to a low temperature of 150°C or below, an image showing the distribution of Sn, and an image showing the distribution of Si. Figure 4 (B) shows a HAADF-STEM image of substrate 10 when the temperature of substrate 10 is set to a high temperature of 150°C or higher, an image showing the distribution of Sn, and an image showing the distribution of Si. Figure 4 As shown in (B), at high temperatures, Sn is not distributed, but Si is distributed; therefore, SnO2 is replaced by SiO2, and the replacement rate is fast. On the other hand, as... Figure 4 As shown in (A), at low temperatures, Sn and Si coexist, resulting in a slow substitution rate.

[0043] For example, when the temperature of the substrate 10 is set to 50°C, 100°C, 150°C, or 200°C and the substrate is exposed to dichlorosilane gas at 5 Torr (666.61 Pa), the replacement rate of SnO2 to SiO2 in the exposed portion 20a of the metal oxide resist film 20 is as follows.

[0044] 50℃: 0.15 [nm / min]

[0045] 100℃: 0.45 [nm / min]

[0046] 150℃: 0.62 [nm / min]

[0047] 200℃: >0.62 [nm / min]

[0048] When the temperature of substrate 10 is set to 200°C, the exposed portion 20a is completely replaced. Therefore, the replacement rate at 200°C is greater than 0.62 nm / min.

[0049] The replacement gradually weaves from the surface of the metal oxide resist film 20 into its interior. The lower the temperature of the substrate 10, the slower the replacement rate, and the longer it takes to replace the entire exposed portion 20a. The temperature of the substrate 10 during replacement only needs to 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 will not be damaged by heat. For example, the temperature of the substrate 10 during replacement is preferably set in the range of 50°C to 500°C. In order to make the replacement proceed rapidly, the temperature of the substrate 10 is preferably 100°C or higher, and more preferably 200°C or higher.

[0050] (Device structure)

[0051] Next, an example of the structure of the substrate processing apparatus 100 according to the embodiment will be described. Figure 5 This is a diagram illustrating an example of the general structure of the substrate processing apparatus 100 according to the embodiment.

[0052] The substrate processing apparatus 100 includes a chamber 110, a gas supply unit 120, a stage 130, and an exhaust unit 140. Additionally, the substrate processing apparatus 100 includes a gas inlet. The chamber 110 is hermetically sealed. The gas inlet is configured to introduce at least one processing gas into the chamber 110. The gas inlet includes a spray head 113. The stage 130 is disposed within the chamber 110. The spray head 113 is disposed above the stage 130. In one embodiment, the spray head 113 constitutes at least a portion of the ceiling of the chamber 110.

[0053] The stage 130 has a mounting surface 130a formed on its upper surface for supporting the substrate 10. The mounting surface 130a is larger than the substrate 10. A loading / unloading outlet (not shown) is provided in the chamber 110. The loading / unloading outlet can be opened and closed by a gate valve. When the substrate 10 is loaded into the substrate processing apparatus 100, the loading / unloading outlet (not shown) in the chamber 110 is set to the open state. The substrate 10 is loaded into the chamber 110 from the loading / unloading outlet by a conveying mechanism such as a conveying arm and placed on the mounting surface 130a of the stage 130.

[0054] The unit 130 has a heater 131 installed inside. The heater 131 is connected to a power supply 132. The power supply 132 supplies power to the heater 131. The heater 131 heats up by the power supplied from the power supply 132. The power supply 132 is configured to control the power supplied to the heater 131. The substrate processing apparatus 100 is configured to control the temperature of the heater 131 by controlling the power supplied from the power supply 132 to the heater 131, thereby controlling the temperature of the substrate 10.

[0055] The spray head 113 is configured to introduce at least one processing gas from the gas supply unit 120 into the chamber 110. The spray head 113 has at least one gas supply port 113a, at least one gas diffusion chamber 113b, and a plurality of gas inlets 113c. The processing gas supplied to the gas supply port 113a passes through the gas diffusion chamber 113b and is then introduced into the chamber 110 through the plurality of gas inlets 113c.

[0056] The gas supply unit 120 includes at least one gas source 121 and at least one flow controller 122. Each flow controller 122 may include, for example, a mass flow controller or a pressure-controlled flow controller. The gas supply unit 120 supplies silicon-containing gas from the gas source 121 to the spray head 113 via the flow controller 122.

[0057] The exhaust section 140 is connected to a gas outlet 110a, for example, located at the bottom of the chamber 110. The exhaust section 140 may include a pressure regulating valve and a vacuum pump. The pressure within the chamber 110 is adjusted by the pressure regulating valve. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0058] The substrate processing apparatus 100 includes a control unit 150. The control unit 150 controls each part of the substrate processing apparatus 100 to enable the substrate processing apparatus 100 to perform substrate processing.

[0059] (Substrate processing)

[0060] Next, an example of substrate processing incorporating the substrate processing method of this disclosure will be described. Figure 6 This is a diagram illustrating an example of the substrate processing flow involved in the embodiment. Figure 6 Show Figure 3 The process of substrate processing in which a pattern is formed on substrate 10 is shown.

[0061] 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, where a metal oxide photoresist film 20, such as a tin oxide film, is formed on the substrate 10. The metal oxide photoresist film 20 can be formed on the substrate 10 by spin coating or by vacuum deposition.

[0062] Next, the substrate 10, on which a photoresist film containing a metal oxide is formed, is subjected to EUV exposure (step S11). For example, the substrate 10 is transported to an EUV exposure apparatus and subjected to EUV exposure in the EUV exposure apparatus. During EUV exposure, EUV light is irradiated onto the metal oxide photoresist film 20 of the substrate 10 through a mask 30 on which a predetermined pattern is formed.

[0063] Next, the substrate 10 after EUV exposure is subjected to post-exposure baking (PEB) (step S12). For example, the substrate 10 is transferred to a heat treatment apparatus and subjected to post-exposure baking in the heat treatment apparatus.

[0064] Next, the substrate 10 after exposure and baking is developed (step S13). For example, the substrate 10 is transported to an etching apparatus, and the pattern formed on the metal oxide resist film 20 is developed by etching the metal oxide resist film 20 of the substrate 10 in the etching apparatus.

[0065] Next, the developed substrate 10 is exposed to a silicon-containing gas (step S14). For example, the substrate 10 is transferred 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 silicon-containing gas via the exhaust section 140. Furthermore, the substrate processing apparatus 100 controls the temperature of the heater 131 to maintain the substrate 10 placed on the stage 130 at a temperature ranging from 50°C to 500°C. Then, the substrate processing apparatus 100 supplies silicon-containing gas into the chamber 110 from the gas supply section 120 to expose the substrate 10 to the silicon-containing gas. For example, the substrate processing apparatus 100 sets the pressure in the chamber 110 to 1 Torr (133.32 Pa) and the temperature of the substrate 10 to 200°C, then exposes the substrate 10 to SiH2Cl2 gas for 20 minutes. As a result, the metal in the metal oxide constituting the developed metal oxide resist film 20 is replaced with silicon. For example, when the metal oxide resist film 20 is set to SnO x In the case of [the substance], it is replaced by SiO2.

[0066] Therefore, conventional SiO2 processing techniques can be used to process the exposed portion 20a. 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.

[0067] Next, an example of processing the patterned substrate 10 will be described. Hereinafter, as an example of processing the substrate 10, the process of substrate processing for double patterning of the substrate 10 will be described. Figure 7 This diagram illustrates an example of a substrate processing flow for double patterning of substrate 10. The metal oxide resist film 20 on substrate 10 is, for example, patterned by... Figure 3 The substrate processing shown involves forming a pattern in the exposure portion 20a. The SnO2 in the exposure portion 20a is replaced with SiO2.

[0068] In the case of double patterning of substrate 10, SiN can be formed on substrate 10, for example, by ALD (Atomic Layer Deposition). x Film 25. SiN is formed on substrate 10 in a manner that covers the unevenness formed by the exposed portion 20a of the metal oxide resist film 20. x Film 25. Next, SiN is formed on substrate 10 by plasma etching or the like. x Anisotropic etching of film 25. This is achieved through SiN etching. x Anisotropic etching of film 25, in substrate 10, the SiN in the upper surface portion of the exposed portion 20a of metal oxide resist film 20 and the recessed portion between the exposed portions 20a. x Film 25 was etched. This was achieved through SiN etching. x Anisotropic etching of film 25, in substrate 10, exposes the SiN on the sidewall portion of portion 20a. x Film 25 is retained. Next, SiO2 is formed on substrate 10 by plasma etching or the like. x Anisotropic etching. This is achieved through SiO2 etching. x Anisotropic etching is performed on the substrate 10, where the exposed portion 20a is etched from the upper surface side, and the SiN as the sidewall portion of the exposed portion 20a is etched. x Film 25 is retained. During the dual patterning of substrate 10, the retained SiN... x The film 25 is used as a mask to pattern the substrate 10. This enables fine processing of the substrate 10.

[0069] In this way, by means of the substrate processing method described in the embodiment, SnO2 in the exposed portion 20a of the metal oxide resist film 20 is replaced with SiO2, thereby enabling dual patterning of the substrate 10.

[0070] Furthermore, in the above embodiments, the case where the metal oxide resist film 20 is a tin oxide film was mainly described as an example. However, the disclosed technology is not limited to this. It is presumed that the substitution shown in the embodiments will occur as long as the element has chain-forming properties. Chain formation refers to the bonding of atoms of the same element into a long chain. For example, the metal oxide resist film 20 may also be a film of oxides of any one of W, Te, Sb, In, Zn, Zr, and Hf. In this case, the oxides of W, Te, Sb, In, Zn, Zr, and Hf contained in the metal oxide resist film 20 can also be replaced with silicon by the substrate processing method according to the embodiments. As a result, the processability of the photoresist film in EUV exposure can be improved.

[0071] Furthermore, in the above embodiment, the substrate processing apparatus 100 was described as an example of a structure in which substrates 10 are exposed one by one to a silicon-containing gas. However, the disclosed technology is not limited to this. The substrate processing apparatus 100 may also be configured to expose multiple substrates 10 to a silicon-containing gas by arranging multiple substrates 10 inside the chamber 110.

[0072] The embodiments have been described above. As described above, the substrate processing method according to the above embodiments includes step (a) (e.g., step S14) and step (b) (e.g., step S14). In step a, a substrate 10 with a photoresist film formed on its surface is disposed in a chamber 110, wherein the photoresist film is a photoresist film containing a metal oxide. In step (b), a silicon-containing gas is supplied into the chamber 110 to replace the metal in the metal oxide constituting the photoresist film with silicon. Therefore, the substrate processing method according to the embodiments can improve the processability of the photoresist film in EUV exposure.

[0073] Furthermore, the photoresist film is a metal oxide photoresist film 20. The substrate processing method according to the embodiment further includes a step (c) before step (a) and step (b). In step (c), the metal oxide photoresist film 20 formed on the surface of the substrate 10 is subjected to EUV exposure. Therefore, the substrate processing method according to the embodiment can improve the processability of the metal oxide photoresist film 20 during EUV exposure.

[0074] Furthermore, the substrate processing method according to the embodiment includes a step (d) after step (c) and before step (b). In step (d), the metal oxide resist film 20 after EUV exposure is developed, before step (b). As a result, the substrate processing method according to the embodiment can improve the processability of the developed metal oxide resist film 20.

[0075] Furthermore, the metal oxide is an oxide of any one of Sn, W, Te, Sb, In, Zn, Zr, and Hf. Therefore, the substrate processing method according to the embodiments can replace the metal constituting the metal oxide with silicon.

[0076] Furthermore, the metal oxide resist film 20 is a tin oxide film. Therefore, the substrate processing method according to the embodiment can replace the tin constituting the tin oxide film with silicon.

[0077] Additionally, the gas contains silicon halides and hydrides. In step (b), the silicon halides and hydrides are brought into contact with the metal oxide contained in the developed metal oxide resist film 20, thereby replacing the metal constituting the metal oxide with silicon. Thus, the substrate processing method according to the embodiment can replace the metal constituting the metal oxide with silicon.

[0078] Furthermore, the silicon halide and the hydride are selected from SiCl4, SiH2Cl2, SiF4, SiH4, Si2H6, and Si2Cl6 to form the silicon oxide. Thus, the substrate processing method according to the embodiments can replace the metal constituting the metal oxide with silicon.

[0079] Furthermore, in step (b), after heating the substrate 10 to 50°C or higher, gas is supplied into the chamber 110 to replace the metal in the metal oxide constituting the photoresist film with silicon. Thus, the substrate processing method according to the embodiment can replace the metal constituting the metal oxide with silicon.

[0080] Furthermore, the substrate processing method according to the embodiment further includes step (e) after step (b). In step (e), a double patterning of the photoresist film is performed. Therefore, the substrate processing method according to the embodiment is able to form fine patterns on the photoresist film.

[0081] Furthermore, 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 within the chamber 110 and holds a substrate 10 on which a photoresist film, comprising a metal oxide, is formed. The gas supply unit 120 supplies silicon-containing gas into the chamber 110. Therefore, the substrate processing apparatus 100 according to the embodiment can improve the processability of the photoresist film during EUV exposure.

[0082] (other)

[0083] Furthermore, the technology disclosed in this application is not limited to the above-described embodiments, and various modifications can be made within the scope of its spirit.

[0084] Furthermore, the embodiments disclosed herein should be considered illustrative rather than restrictive in all respects. In fact, the above-described embodiments can be implemented in various ways. In addition, the above-described embodiments can be omitted, substituted, or modified in various ways without departing from the appended claims and their spirit.

[0085] In addition, the following notes are disclosed regarding the above-described embodiments.

[0086] (Note 1)

[0087] A substrate processing method, comprising:

[0088] Step (a) involves placing a substrate with a photoresist film formed on its surface inside a cavity, wherein the photoresist film is a photoresist film comprising a metal oxide; and

[0089] Step (b) involves supplying a silicon-containing gas into the chamber to replace the metal in the metal oxide that constitutes the photoresist film with silicon.

[0090] (Note 2)

[0091] According to the substrate processing method described in Appendix 1, wherein,

[0092] The photoresist film is a metal oxide photoresist film.

[0093] The substrate processing method further includes step (c), which involves exposing the metal oxide resist film formed on the surface of the substrate to EUV (Extreme Ultraviolet) exposure before steps (a) and (b).

[0094] (Note 3)

[0095] According to the substrate processing method described in Appendix 2, wherein,

[0096] It also includes step (d), which is performed after step (c) and before step (b), to develop the metal oxide resist film after EUV exposure.

[0097] (Note 4)

[0098] According to any one of Appendices 1 to 3, in the substrate processing method, wherein,

[0099] The metal oxide is an oxide of any one of Sn, W, Te, Sb, In, Zn, Zr, and Hf.

[0100] (Note 5)

[0101] According to the substrate processing method described in Appendix 2 or 3, wherein,

[0102] The metal oxide resist film is a tin oxide film.

[0103] (Note 6)

[0104] According to the substrate processing method described in Appendix 3, wherein...

[0105] The gas contains silicon halides and hydrides.

[0106] In step (b), silicon halides and hydrides are brought into contact with the metal oxide contained in the developed metal oxide resist film, so that silicon replaces the metal constituting the metal oxide.

[0107] (Note 7)

[0108] According to the substrate processing method described in Appendix 6, wherein...

[0109] The silicon halide and the hydride are selected from SiCl4, SiH2Cl2, SiF4, SiH4, Si2H6, and Si2Cl6, and are used to form silicon oxide.

[0110] (Postscript 8)

[0111] According to any one of Appendices 1 to 7, in the substrate processing method, wherein,

[0112] In step (b), the substrate is heated to 50°C or higher, and the gas is supplied into the chamber to replace the metal in the metal oxide constituting the photoresist film with silicon.

[0113] (Note 9)

[0114] According to any one of Appendices 1 to 8, in the substrate processing method, wherein,

[0115] It also includes step (e), which, after step (b), performs double patterning of the photoresist film.

[0116] (Postscript 10)

[0117] A substrate processing apparatus comprising:

[0118] Chamber;

[0119] A platform, disposed within the cavity, holds a substrate on which a photoresist film has been formed on its surface, the photoresist film being a photoresist film comprising a metal oxide; and

[0120] A gas supply unit supplies silicon-containing gas into the chamber.

[0121] Explanation of reference numerals in the attached figures

[0122] 10: Substrate

[0123] 11: Silicon substrate

[0124] 12: First lower membrane

[0125] 13: Second lower layer membrane

[0126] 20: Metal oxide resist film

[0127] 20a: Exposure section

[0128] 20b: Unexposed portion

[0129] 25: SiN x membrane

[0130] 30: Mask

[0131] 100: Substrate processing apparatus

[0132] 110: Chamber

[0133] 120: Gas Supply Department

[0134] 130: Taiwan

[0135] 130a: Placement surface

[0136] 131: Heater

[0137] 132: Power supply

[0138] 140: Exhaust section

[0139] 150: Control Department

Claims

1. A substrate processing method, comprising: In step (a), a substrate with a photoresist film formed on its surface is disposed in a cavity, wherein the photoresist film is a photoresist film containing a metal oxide. as well as Step (b) involves supplying a silicon-containing gas into the chamber to replace the metal in the metal oxide that constitutes the photoresist film with silicon.

2. The substrate processing method according to claim 1, wherein, The photoresist film is a metal oxide photoresist film. The substrate processing method further includes step (c), which involves exposing the metal oxide resist film formed on the surface of the substrate to extreme ultraviolet (EUV) light before steps (a) and (b).

3. The substrate processing method according to claim 2, wherein, It also includes step (d), which is performed after step (c) and before step (b), to develop the metal oxide resist film after EUV exposure.

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

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

6. The substrate processing method according to claim 3, wherein, The gas contains silicon halides and hydrides. In step (b), silicon halides and hydrides are brought into contact with the metal oxide contained in the developed metal oxide resist film, so that silicon replaces the metal constituting the metal oxide.

7. The substrate processing method according to claim 6, wherein, The silicon halide and the hydride are selected from SiCl4, SiH2Cl2, SiF4, SiH4, Si2H6, and Si2Cl6, and are used to form silicon oxide.

8. The substrate processing method according to claim 1, wherein, In step (b), the substrate is heated to 50°C or higher, and the gas is supplied into the chamber to replace the metal in the metal oxide constituting the photoresist film with silicon.

9. The substrate processing method according to claim 1, wherein, It also includes step (e), which, after step (b), performs double patterning of the photoresist film.

10. A substrate processing apparatus comprising: Chamber; A platform, disposed within the cavity, is placed on a substrate on which a photoresist film is formed on the surface, the photoresist film being a photoresist film containing a metal oxide. as well as A gas supply unit supplies silicon-containing gas into the chamber.

Images