Substrate processing method

Abstract

To provide a substrate processing method for forming a mask of a positive pattern.SOLUTION: A substrate processing method includes the steps for: preparing a substrate which has a photoresist film that contains a metal oxide containing a first metal element; performing light exposure processing on the substrate so as to form an exposed part and an unexposed part in the photoresist film; supplying a metal-containing gas which contains a second metal element different from the first metal element to the substrate so as to form a metal oxide film that contains the second metal element on the exposed surface of the unexposed part; and removing the exposed part of the photoresist film using the metal oxide film as a mask.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a substrate processing method.

Background Art

[0002] Patent Document 1 discloses a method for manufacturing a semiconductor device, which includes a step of depositing an organic insulating film on a semiconductor substrate, a step of selectively forming a silylated layer on the organic insulating film, and a step of etching the organic insulating film using the silylated layer as a mask to form a recess serving as a connection hole or a wiring groove in the organic insulating film.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] On one side, the present disclosure provides a substrate processing method for forming a positive pattern mask.

Means for Solving the Problems

[0005] To solve the above problems, a substrate having a photoresist film containing a metal oxide containing a first metal element is prepared, the substrate is exposed to form an exposed portion and an unexposed portion in the photoresist film, a metal-containing gas containing a second metal element different from the first metal element is supplied to the substrate to form a metal oxide film containing the second metal element on the exposed surface of the unexposed portion, and the exposed portion of the photoresist film is removed using the metal oxide film as a mask. A substrate processing method is provided.

Effects of the Invention

[0006] According to one aspect, a substrate processing method for forming a positive pattern mask can be provided.

Brief Description of the Drawings

[0007]

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Modes for Carrying Out the Invention

[0008] Hereinafter, modes for carrying out the present disclosure will be described with reference to the drawings. In each drawing, the same reference numerals are given to the same components, and redundant descriptions may be omitted.

[0009] <First Embodiment> An example of the substrate processing method according to the first embodiment will be described with reference to FIGS. 1 to 6. FIG. 1 is a flowchart showing an example of the substrate processing method according to the first embodiment. FIGS. 2 to 6 are examples of schematic diagrams of the substrate in each step. Note that FIG. 2 is a schematic cross-sectional view of the substrate. Further, in FIGS. 3 to 6, (b) is a schematic view of the substrate seen from above. (a) is a schematic cross-sectional view taken along the line A-A of (b). Note that although (b) is a view seen from above, each component is illustrated with the same hatching as the cross-section of (a).

[0010] In step S101, a substrate is prepared. Here, the prepared substrate includes an underlayer film 310 (see FIG. 2). The underlayer film 310 is a film disposed under a photoresist film 320 (see FIG. 2) described later. Further, the underlayer film 310 is a film on which the pattern of an opening 325 described later is formed as a mask 320A (see FIG. 6), and the opening pattern of the mask 320A is transferred by an etching process. The underlayer film 310 may be, for example, a silicon-containing film (such as a SOG (Spin On Glass) film), a carbon-containing film (such as a SOC (Spin On Carbon) film), or the like. Further, the underlayer film 310 may be a laminated film in which a plurality of films such as a silicon-containing film and a carbon-containing film are laminated. Further, the underlayer film 310 as a laminated film may have a film such as an anti-reflection film (BARC: Bottom Anti-Reflective Coating). The underlayer film 310 may be, for example, a film used as a hard mask.

[0011] In step S102, a process of forming a photoresist film 320 on the substrate is performed. FIG. 2 is an example of a schematic diagram of the substrate after the formation of the photoresist film 320.

[0012] Here, a photoresist film 320 is formed on the base film 310. The photoresist film 320 is a film containing a metal oxide containing a first metal element. Further, the photoresist film 320 may be a metal oxide resist containing a first metal element, or may be a resin resist (chemically amplified resist (CAR)) using a metal oxide containing a first metal element as a sensitizer, and is not limited thereto. Here, the first metal element includes any one or more of Sn, W, Te, Zn, Zr, Sb, In, etc. The metal oxide is, for example, SnO x (x is an arbitrary number), WO x (x is an arbitrary number), TeO x (x is an arbitrary number), ZnO x (x is an arbitrary number), ZrO x (x is an arbitrary number), SbO x (x is an arbitrary number), InO x (x is an arbitrary number), etc. Further, in the exposure process (see S103) described later, the valence or oxidation number of the first metal element changes due to EUV (Extreme Ultraviolet) exposure in the photoresist film 320. Further, the photoresist film 320 is a negative photoresist film.

[0013] In step S103, the substrate is subjected to an exposure process. FIG. 3 is an example of a schematic diagram of the substrate after the exposure process.

[0014] Here, in a nitrogen atmosphere, EUV is irradiated onto the photoresist film 320 of the substrate through a photomask (not shown) having a predetermined pattern. As a result, as shown in FIG. 3, an exposed portion 321 irradiated with EUV and an unexposed portion 322 not irradiated with EUV are formed on the photoresist film 320. As shown in FIG. 10 to be described later, the photoresist film 320 may have a reaction layer 321a (fully exposed portion) on the central side of the exposed portion 321 and an unreacted substance-containing layer 321b (intermediate exposed portion) on the outer peripheral side of the exposed portion 321. The reaction layer 321a is a region where EUV is sufficiently exposed and the valence or oxidation number of the first metal element is changed by EUV. The unreacted substance-containing layer 321b is a region where the exposure of EUV is insufficient and a part of the first metal element whose valence or oxidation number has not changed remains. In the unexposed portion 322, EUV exposure has not been performed, and the first metal element whose valence or oxidation number has not changed remains.

[0015] In step S104, a process of selectively forming a metal oxide film 330 on the upper surface (exposed surface) of the unexposed portion 322 of the photoresist film 320 is performed. FIG. 4 is an example of a schematic diagram of the substrate after the selective film formation process of the metal oxide film 330. The process of selectively forming the metal oxide film 330 will be described later with reference to FIGS. 7 to 8. As a result, the metal oxide film 330 is formed on the upper surface of the unexposed portion 322. When the exposed portion 321 has a reaction layer 321a (fully exposed portion) and an unreacted substance-containing layer 321b (intermediate exposed portion), the metal oxide film 330 is formed on the upper surfaces of the unexposed portion 322 and the unreacted substance-containing layer 321b (intermediate exposed portion).

[0016] In step S105, a resist etching process is performed. FIG. 5 is an example of a schematic diagram of the substrate after the resist etching process.

[0017] Here, an etching process is performed on the photoresist film 320 using the metal oxide film 330 as a mask. As a result, the exposed portion 321 is etched to form a mask 320A having an opening 325. When the exposed portion 321 has a reaction layer 321a (fully exposed portion) and an unreacted substance-containing layer 321b (intermediate exposed portion), the reaction layer 321a (fully exposed portion) is etched to form a mask 320A having an opening 325.

[0018] In step S106, a metal oxide film etching process is performed. FIG. 6 is an example of a schematic diagram of a substrate after the metal oxide film etching process. Here, the metal oxide film 330 is removed by the etching process. If the metal oxide film 330 does not affect other processes or the like, the process of step S106 may be omitted.

[0019] As described above, according to the substrate processing method shown in FIG. 2, a mask 320A having an opening 325 for the portion exposed in the exposure process (S103) can be formed on the substrate. That is, a positive-pattern mask 320A can be formed on the substrate.

[0020] Next, the process shown in step S104 will be described with reference to FIGS. 7 to 8.

[0021] First, an example of a substrate processing apparatus for performing the process shown in step S104 on the substrate W will be described with reference to FIG. 7. FIG. 7 is a schematic diagram showing an example of a substrate processing apparatus.

[0022] The substrate processing apparatus includes a processing chamber 1, a mounting stage 2, a shower head 3, an exhaust unit 4, a gas supply unit 5, and a control unit 6.

[0023] The processing container 1 is made of a metal such as aluminum and has a substantially cylindrical shape. The processing container 1 houses the substrate W. An inlet / outlet 11 for loading or unloading the substrate W is formed in the side wall of the processing container 1. The inlet / outlet 11 is opened and closed by a gate valve 12. An annular exhaust duct 13 with a rectangular cross-section is provided on the main body of the processing container 1. A slit 13a is formed along the inner peripheral surface of the exhaust duct 13. An exhaust port 13b is formed in the outer wall of the exhaust duct 13. A top wall 14 is provided on the upper surface of the exhaust duct 13 so as to close the upper opening of the processing container 1. The space between the exhaust duct 13 and the top wall 14 is hermetically sealed by a seal ring 15.

[0024] The mounting table 2 horizontally supports the substrate W inside the processing container 1. The mounting table 2 has a disk shape larger than the substrate W and is made of a ceramic material such as aluminum nitride (AlN), or a metal material such as aluminum or nickel alloy. A heater 21 for heating the substrate W is embedded inside the mounting table 2. The heater 21 is powered from a heater power supply (not shown) and generates heat. Then, the output of the heater 21 is controlled by the temperature signal of a thermocouple (not shown) provided near the upper surface of the mounting table 2, so that the substrate W is controlled to a predetermined temperature. The mounting table 2 is provided with a cover member 22 formed of a ceramic such as alumina so as to cover the outer peripheral region and the side surface of the upper surface.

[0025] The mounting table 2 is supported by a support member 23. The support member 23 extends downward from the center of the bottom surface of the mounting table 2 through a hole formed in the bottom wall of the processing container 1 and extends below the processing container 1, and its lower end is connected to an elevating mechanism 24. The mounting table 2 is moved up and down by the elevating mechanism 24 between the processing position shown by the solid line in FIG. 7 and the transfer position below the substrate W shown by the two-dot chain line where the substrate W can be transferred. A flange portion 25 is attached below the processing container 1 of the support member 23. A bellows 26 is provided between the bottom surface of the processing container 1 and the flange portion 25. The bellows 26 partitions the atmosphere inside the processing container 1 from the outside air and expands and contracts as the mounting table 2 moves up and down.

[0026] Near the bottom surface of the processing container 1, three (only two are shown) wafer support pins 27 are provided so as to protrude upward from the lifting plate 27a. The wafer support pins 27 are lifted and lowered via the lifting plate 27a by a lifting mechanism 28 provided below the processing container 1. The wafer support pins 27 are inserted into through holes 2a provided in the mounting table 2 at the transfer position and can protrude and retract with respect to the upper surface of the mounting table 2. By raising and lowering the wafer support pins 27, the substrate W is transferred between a transfer robot (not shown) and the mounting table 2.

[0027] The shower head 3 supplies the processing gas in a shower shape into the processing container 1. The shower head 3 is formed of, for example, a metal material and is disposed to face the mounting table 2. The shower head 3 has substantially the same diameter as the mounting table 2. The shower head 3 includes a main body portion 31 and a shower plate 32. The main body portion 31 is fixed to the lower surface of the top wall 14. The shower plate 32 is connected below the main body portion 31. A gas diffusion space 33 is formed between the main body portion 31 and the shower plate 32. A gas introduction hole 36 is provided in the gas diffusion space 33 so as to penetrate the centers of the top wall 14 and the main body portion 31. An annular protrusion 34 protruding downward is formed at the peripheral edge of the shower plate 32. A large number of gas discharge holes 35 are formed on the flat surface inside the annular protrusion 34 of the shower plate 32.

[0028] When the mounting table 2 is in the processing position, a processing space 38 is formed between the mounting table 2 and the shower plate 32, and the upper surface of the cover member 22 and the annular protrusion 34 are close to each other to form an annular gap 39.

[0029] The exhaust section 4 exhausts the inside of the processing container 1. The exhaust section 4 includes an exhaust pipe 41 and an exhaust mechanism 42. The exhaust pipe 41 is connected to the exhaust port 13b. The exhaust mechanism 42 is connected to the exhaust pipe 41 and includes a vacuum pump, a pressure control valve, and the like. The exhaust mechanism 42 exhausts the gas in the processing container 1 via the exhaust duct 13 and the exhaust pipe 41.

[0030] The gas supply unit 5 supplies various gases to the shower head 3. The gas supply unit 5 has a gas supply source 51. The gas supply source 51 supplies various process gases from the gas introduction hole 36, through the gas diffusion space 33, to the process space 38 from the gas discharge hole 35.

[0031] The control unit 6 is, for example, a computer, and includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), an auxiliary storage device, etc. The CPU operates based on a program stored in the ROM or the auxiliary storage device, and controls the operation of the substrate processing apparatus. The control unit 6 may be provided inside the substrate processing apparatus, or may be provided outside. When the control unit 6 is provided outside the substrate processing apparatus, the control unit 6 can control the substrate processing apparatus through a communication network such as wired or wireless.

[0032] Next, an example of the film formation process of the substrate processing apparatus will be described with reference to FIG. 8. FIG. 8 is a flowchart showing an example of the film formation process of the substrate processing apparatus.

[0033] In step S201, a substrate is prepared. Here, as shown in FIG. 3, the prepared substrate has an exposed portion 321 and an unexposed portion 322 in the photoresist film 320.

[0034] In step S202, a metal-containing gas containing a second metal element different from the first metal element is supplied to the substrate as a precursor gas (film-forming gas). Here, the control unit 6 controls the gas supply unit 5 to supply the metal-containing gas containing the second metal element into the processing container 1. The second metal element includes any one or more of Al, Ti, Ga, Ru, Hf, Sn, W, Te, Zn, Zr, Sb, In, etc., as long as it is not used as the first metal element. In other words, when any one of "Sn, W, Te, Zn, Zr, Sb, In" is selected as the first metal element, the second metal element may be selected from among "Al, Ti, Ga, Ru, Hf" and those excluding the element selected as the first metal element from "Sn, W, Te, Zn, Zr, Sb, In". Examples of the metal-containing gas containing the second metal element include TMA (trimethylaluminum), TDMAT (tetrakis(dimethylamino)titanium), TEGa (triethylgallium), Ru3CO 12 and includes any one or more of the like. Also, by setting the temperature of the metal-containing gas to be lower than the temperature at which a film is formed by thermal decomposition, the formation of the metal oxide film 330 on the upper surface of the exposed portion 321 is suppressed.

[0035] On the other hand, on the upper surface of the unexposed portion 322, the precursor of the metal-containing gas is decomposed by reacting with the metal-containing gas containing the second metal element using the first metal element whose valence or oxidation number did not change and remained in the unexposed portion 322 as a catalyst, and a metal oxide film (metal-containing film) 330 is selectively formed on the upper surface of the unexposed portion 322.

[0036] In step S203, an inert gas is supplied to the substrate. The control unit 6 controls the gas supply unit 5 to supply the inert gas into the processing container 1. The inert gas is a gas that is inert to the photoresist film 320 and the metal-containing gas. The inert gas includes any one or more of nitrogen (N2) gas, Ar gas, He gas, etc. Here, the metal-containing gas physically adsorbed on the upper surface of the exposed portion 321 or the like is purged with the inert gas.

[0037] In step S204, the control unit 6 determines whether or not the processes of steps S202 and S203 have been repeated a predetermined number of times. If they have not been repeated the predetermined number of times (S204·NO), the process of the control unit 6 returns to step S202 and repeats. Here, when the film thickness of the metal oxide film 330 reaches a predetermined film thickness (for example, about 1 nm), the catalytic effect of the unexposed portion 322 disappears and the growth of the metal oxide film 330 stops. Thereby, the film thickness of the metal oxide film 330 can be suitably controlled. Then, when the processes have been repeated the predetermined number of times (S204·YES), the process of the control unit 6 ends.

[0038] As described above, according to the film formation method shown in FIG. 8, the metal oxide film 330 can be selectively formed on the upper surface of the unexposed portion 322 with respect to the upper surface of the exposed portion 321. When the exposed portion 321 has the reaction layer 321a (completely exposed portion) and the unreacted substance-containing layer 321b (intermediate exposed portion), the metal oxide film 330 can be selectively formed on the upper surface of the unexposed portion 322 and the upper surface of the unreacted substance-containing layer 321b (intermediate exposed portion) with respect to the upper surface of the reaction layer 321a (completely exposed portion).

[0039] In step S202, although the description has been given assuming that a metal-containing gas containing a second metal element is supplied as a precursor gas (film-forming gas) to form a metal oxide film 330 containing the second metal element on the upper surfaces of the unexposed portion 322 and the unreactant-containing layer 321b, the present invention is not limited thereto. Instead of the metal-containing gas, a semiconductor gas containing any one or more semiconductor raw materials (semiconductor elements) such as Si, B, Ge, Se, etc. may be supplied into the processing vessel 1, and a semiconductor film (not shown) containing a semiconductor raw material (semiconductor element) different from the first metal element may be formed on the upper surfaces of the unexposed portion 322 and the unreactant-containing layer 321b. That is, in step S202, either the metal-containing gas containing the second metal element or the semiconductor gas containing the semiconductor raw material may be supplied. Thereby, a configuration may be adopted in which a semiconductor film (not shown) containing a semiconductor raw material (semiconductor element) is selectively formed on the upper surfaces of the unexposed portion 322 and the unreactant-containing layer 321b. Further, the present invention is not limited thereto, and in step S202, both the metal-containing gas containing the second metal element and the semiconductor gas containing the semiconductor raw material may be supplied.

[0040] <Second Embodiment> An example of a substrate processing method according to the second embodiment will be described with reference to FIGS. 9 to 14. FIG. 9 is a flowchart showing an example of the substrate processing method according to the second embodiment. FIGS. 10 to 14 are examples of schematic views of the substrate in each step. In FIGS. 10 to 14, (b) is a schematic view of the substrate seen from above. (a) is a cross-sectional schematic view taken along line A-A of (b). Although (b) is a view seen from above, each component is shown with the same hatching as the cross-section of (a).

[0041] In step S301, a substrate is prepared. Here, the prepared substrate includes an underlayer film 310 (see FIG. 2). The underlayer film 310 is a film disposed under a photoresist film 320 (see FIG. 2) described later. Further, the underlayer film 310 is a film on which the pattern of an opening 335 described later is formed, and the opening pattern of the mask is transferred by an etching process using a metal oxide film 330 (see FIG. 14) as a mask. The underlayer film 310 may be, for example, a silicon-containing film (such as a SOG (Spin On Glass) film), a carbon-containing film (such as a SOC (Spin On Carbon) film), or the like. Further, the underlayer film 310 may be a laminated film in which a plurality of films such as a silicon-containing film and a carbon-containing film are laminated. Further, the underlayer film 310 as a laminated film may have a film such as an anti-reflection film (BARC: Bottom Anti-Reflective Coating). The underlayer film 310 may be, for example, a film used as a hard mask.

[0042] In step S302, a process of forming a photoresist film 320 on the substrate is performed. FIG. 2 is an example of a schematic diagram of the substrate after the formation of the photoresist film 320.

[0043] Here, a photoresist film 320 is formed on the underlayer film 310. The photoresist film 320 is a film containing a metal oxide containing a first metal element. Further, the photoresist film 320 may be a metal oxide resist containing a first metal element, or may be a resin resist (chemically amplified resist (CAR)) using a metal oxide containing a first metal element as a sensitizer, and is not limited thereto. Here, the first metal element includes any one or more of Sn, W, Te, Zn, Zr, Sb, In, etc. The metal oxide is, for example, SnO x (x is an arbitrary number), WO x (x is an arbitrary number), TeO x (x is an arbitrary number), ZnO x (x is an arbitrary number), ZrO x (x is an arbitrary number), SbO x (x is an arbitrary number), InO xIt may be any of (x is an arbitrary number) or the like. Further, in the exposure process (see S103) described later, the valence or oxidation number of the first metal element changes due to the exposure of EUV (Extreme Ultraviolet). Further, the photoresist film 320 is a negative photoresist film.

[0044] In step S303, the substrate is subjected to an exposure process. FIG. 10 is an example of a schematic diagram of the substrate after the exposure process.

[0045] Here, in a nitrogen atmosphere, EUV is irradiated onto the photoresist film 320 of the substrate through a photomask (not shown) having a predetermined pattern. As a result, as shown in FIG. 10, an exposed portion 321 irradiated with EUV and an unexposed portion 322 not irradiated with EUV are formed in the photoresist film 320. Here, as shown in FIG. 10, in the photoresist film 320, a reaction layer 321a (fully exposed portion) is formed on the central side of the exposed portion 321, and an unreacted substance-containing layer 321b (intermediate exposed portion) is formed on the outer peripheral side of the exposed portion 321. The reaction layer 321a is a region where EUV is sufficiently exposed and the valence or oxidation number of the first metal element changes due to EUV. The unreacted substance-containing layer 321b is a region where the exposure of EUV is insufficient and a part of the first metal element whose valence or oxidation number has not changed remains. In the unexposed portion 322, EUV has not been exposed, and the first metal element whose valence or oxidation number has not changed remains.

[0046] In step S304, the substrate is subjected to a development process. FIG. 11 is an example of a schematic diagram of the substrate after the development process.

[0047] Here, by the development process, the unexposed portion 322 of the photoresist film 320 and a part of the unreacted substance-containing layer 322b are selectively removed. The development process can use at least one of a wet process and a dry process. As a result, as shown in FIG. 11, the photoresist film 320 (see FIG. 2) becomes a photoresist film 320B having a pattern of openings 325. Note that the sidewalls of the openings 325 of the photoresist film 320B are formed of the remaining portion of the unreacted substance-containing layer 322b.

[0048] In step S305, a process of selectively forming a metal oxide film 330 is performed from the sidewalls of the openings 325 of the photoresist film 320B.

[0049] First, a process of selectively forming a metal oxide film 330 is performed on the sidewalls of the openings 325 of the photoresist film 320B. FIG. 12 is an example of a schematic diagram of a substrate after the selective formation of the metal oxide film 330. Here, by the process shown in FIG. 8, the metal oxide film 330 can be selectively formed on the exposed surface (upper surface) of the reaction layer 321a (fully exposed portion) and the exposed surface (sidewalls of the openings 325) of the unreacted substance-containing layer 321b (intermediate exposed portion).

[0050] Next, a process of growing the metal oxide film 330 formed on the sidewalls of the openings 325 of the photoresist film 320B is performed. FIG. 13 is an example of a schematic diagram of a substrate after the growth of the metal oxide film 330. Here, the metal oxide film 330 is grown by the ALD (Atomic Layer Deposition) method by alternately supplying a metal-containing gas and a reaction gas (oxidizing gas) to the substrate, and the openings 325 of the photoresist film 320B are filled with the metal oxide film 330. Note that the metal oxide film 330 may be selectively grown in the lateral direction starting from the metal oxide film 330 formed on the sidewalls of the openings 325 in step S305. Further, the film formation method of filling the openings 325 of the photoresist film 320B with the metal oxide film 330 is not limited to this, and for example, a configuration in which a film is filled from the bottom of the openings 325 using a fluid film may be used.

[0051] Note that the metal-containing gas may be the same gas as the gas supplied in step S202. Further, the metal contained in the metal-containing gas may be any one of B, Al, Si, Ti, V, Mn, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ru, Pd, In, Sb, Te, Hf, Ta, W, Pt, and Bi. Further, the oxidizing gas may be any one of water vapor, oxygen, and ozone.

[0052] In step S306, a resist etching process is performed. FIG. 14 is an example of a schematic diagram of the substrate after the resist etching process.

[0053] Here, the photoresist film 320B is removed by an etching process. Thereby, a metal oxide film 330 having an opening 335 is formed. The etching gas may be any one of H2, HF, HCl, HBr, HI, F2, Cl2, Br2, I2, BCl3, CH4, C x -H y 、C x -Cl y 、C x -Br y 、organic acid (such as carboxylic acid gas), halosilane (Si-Cl x 、Si-H x -Cl y ), where x and y are arbitrary numbers.

[0054] As described above, according to the substrate processing method shown in FIG. 9, the metal oxide film 330 having the opening 335 corresponding to the exposed portion in the exposure process (S303) can be formed on the substrate as a mask. That is, a positive pattern mask (metal oxide film 330 having an opening 335) can be formed on the substrate.

[0055] Note that the substrate processing apparatus shown in FIG. 7 has been described as an apparatus that performs a selective film formation process (S104, S305), but it is not limited thereto. In addition to the selective film formation process (S104, S305), a configuration may be adopted in which any one or more of a development process (S304) and an etching process (S105, S106, S306) are performed by the substrate processing apparatus shown in FIG. 7.

[0056] Further, the apparatus for performing the selective film formation process (S104, S305), the apparatus for performing the development process (S304), and the apparatus for performing the etching process (S105, S106, S306) may each be constituted by a different apparatus, or may be a substrate processing apparatus that connects these apparatuses with the same transfer apparatus.

[0057] As described above, the substrate processing method according to the present embodiment has been described. However, the present disclosure is not limited to the above-described embodiments and the like, and various modifications and improvements are possible within the scope of the gist of the present disclosure described in the claims.

Explanation of Reference Numerals

[0058] 310 Underlayer film 320, 320B Photoresist film 320A Mask 321 Exposed portion 321a Reaction layer 321b Unreacted substance-containing layer 322 Unexposed portion 325 Opening 330 Metal oxide film 335 Opening

Claims

1. Preparing a substrate having a photoresist film containing a metal oxide containing a first metal element; Performing an exposure process on the substrate to form an exposed portion and an unexposed portion in the photoresist film; Supplying a metal-containing gas containing a second metal element different from the first metal element to the substrate to form a metal oxide film containing the second metal element on the exposed surface of the unexposed portion; Removing the exposed portion of the photoresist film using the metal oxide film as a mask; and A substrate processing method.

2. The exposure process is Exposing with extreme ultraviolet light to form the exposed portion and the unexposed portion in the photoresist film, The exposed portion is A reaction layer which is a region where the valence or oxidation number of the first metal element is changed by the extreme ultraviolet light, and An unreacted substance-containing layer which is a region where the first metal element whose valence or oxidation number has not changed remains; and The substrate processing method according to Claim 1.

3. The step of forming the metal oxide film is Using the first metal element whose valence or oxidation number has not changed in the unexposed portion and the unreacted substance-containing layer as a catalyst to form the metal oxide film containing the second metal element on the exposed surfaces of the unexposed portion and the unreacted substance-containing layer; The substrate processing method according to Claim 2.

4. Preparing a substrate having a photoresist film containing a metal oxide containing a first metal element; Performing an exposure process and a development process on the substrate to form an opening pattern in the photoresist film; Supplying a metal-containing gas containing a second metal element different from the first metal element to the substrate to form a metal oxide film containing the second metal element from the side wall of the opening of the photoresist film; Removing the photoresist film; and A substrate processing method.

5. The exposure process is Exposing with extreme ultraviolet light to form an exposed portion and an unexposed portion in the photoresist film, The exposed portion is A reaction layer which is a region where the valence or oxidation number of the first metal element is changed by the extreme ultraviolet light, and An unreacted substance-containing layer which is a region where the first metal element whose valence or oxidation number has not changed remains; and The substrate processing method according to Claim 4.

6. The development process is Removing a part of the unexposed portion and the unreacted substance-containing layer; The substrate processing method according to Claim 5.

7. The step of forming the metal oxide film is Using the first metal element whose valence or oxidation number in the unreacted substance-containing layer has not changed as a catalyst, a metal oxide film containing the second metal element is formed on the exposed surface of the unreacted substance-containing layer. The substrate processing method according to claim 6.

8. After the step of forming the metal oxide film, The method further includes a step of supplying an inert gas to the substrate. The substrate processing method according to claim 3 or claim 7.

9. The step of forming the metal oxide film includes: A step of supplying a metal-containing gas containing the second metal element to form the metal oxide film containing the second metal element on the exposed surface of the unreacted substance-containing layer; Alternately supplying a metal-containing gas containing the second metal element and an oxidizing gas to grow the metal oxide film. The substrate processing method according to claim 7.

10. The first metal element includes any one of Sn, W, Te, Zn, Zr, Sb, and In. The substrate processing method according to claim 1 or claim 4.

11. The second metal element includes any one of Al, Ti, Ga, Ru, Hf, and Sn, W, Te, Zn, Zr, Sb, and In only when not used as the first metal element. The substrate processing method according to claim 1 or claim 4.

12. Instead of the step of forming a metal oxide film containing the second metal element, The method includes a step of supplying a semiconductor gas containing a semiconductor raw material to the substrate to form a semiconductor film containing the semiconductor raw material different from the first metal element on the sidewall of the photoresist film. The substrate processing method according to claim 1.

13. The semiconductor raw material includes any one of Si, B, Ge, and Se. The substrate processing method according to claim 12.

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