SUBSTRATE PROCESSING METHOD AND SUBSTRATE PROCESSING SYSTEM

Abstract

The present invention provides a technology for adjusting the shape of a development pattern.　Provided is a substrate processing method. This method includes: (a) a step for providing, on a substrate support part, a substrate having a base film and a metal-containing resist film on the base film, the metal-containing resist film including a first region and a second region; and (b) a step for developing the metal-containing resist film and selectively removing the second region from the metal-containing resist film. The step (b) includes: (b1) a step for removing the second region with respect to the first region at a first selection ratio; and (b2) a step for further removing the second region with respect to the first region at a second selection ratio different from the first selection ratio.

Description

[Technical field]

[0001] Exemplary embodiments of the present disclosure relate to a substrate processing method and a substrate processing system. [Background technology]

[0002] Patent Document 1 discloses a technique for forming a thin film that can be patterned on a semiconductor substrate using extreme ultraviolet light (hereinafter, abbreviated as "EUV"). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2021-523403 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides techniques for adjusting the shape of the developed pattern. [Means for solving the problem]

[0005] In one exemplary embodiment of the present disclosure, there is provided a substrate processing method comprising: (a) providing a substrate having an undercoat film and a metal-containing resist film on a substrate support, the metal-containing resist film including a first region and a second region; and (b) developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film, the step (b) comprising: (b1) removing the second region with a first selectivity relative to the first region; and (b2) further removing the second region with a second selectivity relative to the first region, the second selectivity being different from the first selectivity. Effect of the Invention

[0006] According to one exemplary embodiment of the present disclosure, a technique for adjusting the shape of a developed pattern can be provided. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a diagram for explaining a configuration example of a heat treatment system. [Diagram 2] FIG. 1 is a diagram for explaining a configuration example in the case where the plasma processing system is used as a development processing system. [Diagram 3] FIG. 1 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus. [Figure 4] FIG. 1 is a diagram for explaining a configuration example of a liquid processing system. [Diagram 5] 1 is a flowchart showing a first method. [Figure 6] 1 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11. [Figure 7] 2 is a diagram showing an example of an undercoat film UF of a substrate W. FIG. [Figure 8] 2 is a diagram showing an example of an undercoat film UF of a substrate W. FIG. [Figure 9] 1 is a diagram showing an example of a cross-sectional structure of a substrate W after development. [Figure 10] 13 is a diagram showing an example of a cross-sectional structure of the substrate W after being processed in step ST120. FIG. [Figure 11] 13 is a diagram showing an example of a cross-sectional structure of the substrate W after being processed in step ST122. FIG. [Figure 12] 11 is a flowchart according to a modified example of the first method. [Figure 13] 11 is a flowchart showing a second method. [Figure 14] 13 is a diagram showing an example of a cross-sectional structure of the substrate W after being processed in step ST220. FIG. [Figure 15] 13 is a diagram showing an example of a cross-sectional structure of the substrate W after being processed in step ST222. FIG. [Figure 16] FIG. 2 is a block diagram for explaining an example of the configuration of a substrate processing system SS. [Figure 17]1 is a flow chart showing a method MT. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Each embodiment of the present disclosure will be described below.

[0009] In one exemplary embodiment, there is provided a substrate processing method including: (a) providing a substrate having an undercoat film and a metal-containing resist film on a substrate support, the metal-containing resist film including a first region and a second region; and (b) developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film, the step (b) including: (b1) removing the second region with a first selectivity relative to the first region; and (b2) further removing the second region with a second selectivity relative to the first region, the second selectivity being different from the first selectivity.

[0010] In one exemplary embodiment, the first region is an exposed region and the second region is an unexposed region.

[0011] In one exemplary embodiment, the second selectivity is higher than the first selectivity.

[0012] In one exemplary embodiment, in step (b), the development is performed by wet development, and step (b) satisfies at least one of the following: the solubility of the metal-containing resist film in the developer used in step (I)(b2) is lower than the solubility of the metal-containing resist film in the developer used in step (b1); the concentration of the developer used in step (II)(b2) is lower than the concentration of the developer used in step (b1); and the temperature of the developer used in step (III)(b2) is lower than the temperature of the developer used in step (b1).

[0013] In one exemplary embodiment, in step (b), development is performed by dry development in a chamber, and step (b) satisfies at least one of the following: the temperature of the substrate support in step (I)(b2) is lower than the temperature of the substrate support in step (b1); the pressure in the chamber in step (II)(b2) is lower than the pressure in the chamber in step (b1); the acidity of the second developing gas used in step (III)(b2) is lower than the acidity of the first developing gas used in step (b1); and the concentration of the second developing gas used in step (IV)(b2) is lower than the concentration of the first developing gas used in step (b1).

[0014] In one exemplary embodiment, (b1) is performed by dry development using a first process gas containing a first developing gas, and (b2) is performed by dry development using a second process gas containing a second developing gas, and the step (b) satisfies at least one of the following: (I) the temperature of the substrate support in the step (b2) is lower than the temperature of the substrate support in the step (b1); (II) the pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1); (III) the acidity of the second developing gas is lower than the acidity of the first developing gas; (IV) the concentration of the second developing gas is lower than the concentration of the first developing gas; and (V) the second process gas contains a protective gas that protects the sidewalls of the first region exposed in the steps (b1) and (b2), and the first process gas does not contain a protective gas or contains a protective gas at a partial pressure lower than the partial pressure of the protective gas contained in the second process gas.

[0015] In one exemplary embodiment, in step (b), the development is performed by dry development using plasma generated in the chamber, and step (b) satisfies at least one of the following: the power level of a source RF signal for plasma generation supplied to the chamber in step (I)(b2) is lower than the power level of the source RF signal in step (b1); and the power or voltage level of a bias signal supplied to the chamber in step (II)(b2) is lower than the power or voltage level of the bias signal in step (b1).

[0016] In one exemplary embodiment, step (b) further comprises, between steps (b1) and (b2), a step of modifying the first region.

[0017] In one exemplary embodiment, modifying the first region includes heating or plasma treating the substrate.

[0018] In one exemplary embodiment, the method for processing a substrate is provided, wherein the step of modifying the first region is performed in the same chamber as step (b1).

[0019] In one exemplary embodiment, the step of modifying the first region is performed in a different chamber than step (b1).

[0020] In one exemplary embodiment, in step (b1), the development is performed by wet development, and in step (b2), the development is performed by dry development.

[0021] In one exemplary embodiment, in step (b), a cycle including steps (b1) and (b2) is repeated multiple times.

[0022] In one exemplary embodiment, the metal-containing resist film comprises at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0023] In one exemplary embodiment, the first region is exposed to EUV light.

[0024] In one exemplary embodiment, the switch from step (b1) to step (b2) is performed based on the depth or aspect ratio of the opening formed in the metal-containing resist film by development.

[0025] In one exemplary embodiment, the first region includes a first portion and a second portion below the first portion and on the undercoat film, and step (b1) is performed until just before the second portion is exposed or until a portion of the second portion is exposed.

[0026] In one exemplary embodiment, (c) after the step (b), the method further includes a step of etching the undercoat film using the metal-containing resist film as a mask.

[0027] In one exemplary embodiment, the method further includes at least one of the steps of: after step (b1) and before step (b2), removing residues of the first region or the second region generated in step (b1); and after step (b2) and before step (c), removing residues of the first region or the second region generated in (b1) and / or (b2).

[0028] In one exemplary embodiment, step (c) is performed in the same chamber used for step (b).

[0029] In one exemplary embodiment, step (c) is performed in a chamber different from the chamber used for step (b).

[0030] In one exemplary embodiment, there is provided a substrate processing method including: (a) providing a substrate having an undercoat film and a metal-containing resist film formed on the undercoat film on a substrate support, the metal-containing resist film having a first exposed region and a second unexposed region; and (b) dry developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film, the step (b) including: (b1) controlling a temperature of the substrate support to a first temperature to remove the second region; and (b2) controlling a temperature of the substrate support to a second temperature lower than the first temperature to remove the second region.

[0031] In one exemplary embodiment, step (b) is a dry developing step using HBr, the first temperature is 20° C. or more and 60° C. or less, and the second temperature is −20° C. or more and 20° C. or less.

[0032] In one exemplary embodiment, a substrate processing method is provided, comprising: (a) providing a substrate having an undercoat film and a metal-containing resist film formed on the undercoat film on a substrate support, the metal-containing resist film having a first exposed region and a second unexposed region; and (b) dry developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film, the step (b) comprising: (b1) removing the second region using a first process gas; and (b2) removing the second region using a second process gas that is less acidic than the first process gas.

[0033] In one exemplary embodiment, the first process gas comprises a halogen-containing inorganic acid and the second process gas comprises an organic acid.

[0034] In one exemplary embodiment, the first process gas includes a halogen-containing inorganic acid and an organic acid at a lower flow rate than the halogen-containing inorganic acid, and the second process gas includes a halogen-containing inorganic acid and an organic acid at a higher flow rate than the halogen-containing inorganic acid.

[0035] In one exemplary embodiment, the halogen-containing inorganic acid comprises at least one selected from the group consisting of HBr gas, HCl gas, BCl3 gas, and HF gas and HI gas.

[0036] In one exemplary embodiment, the organic acid comprises at least one selected from the group consisting of a carboxylic acid, a β-dicarbonyl compound, and an alcohol.

[0037] In one exemplary embodiment, step (b) satisfies at least one of the following: the temperature of the substrate support in step (I)(b2) is lower than the temperature of the substrate support in step (b1); and the pressure in the chamber in step (II)(b2) is lower than the pressure in the chamber in step (b1).

[0038] In one exemplary embodiment, in step (b), steps (b1) and (b2) are repeated.

[0039] In one exemplary embodiment, in step (b), a cycle including steps (b1) and (b2) is carried out one or more times, and then step (b1) is further carried out.

[0040] In one exemplary embodiment, step (b) includes removing the second region using plasma generated from the first process gas and / or the second process gas after a cycle including steps (b1) and (b2) has been performed one or more times without using plasma.

[0041] In one exemplary embodiment, there is provided a substrate processing system having one or more substrate processing apparatuses and a controller, wherein the controller is configured to control the one or more substrate processing apparatuses to (a) provide a substrate having an undercoat film and a metal-containing resist film on the undercoat film onto a substrate support, the metal-containing resist film including a first region and a second region, and (b) develop the metal-containing resist film to selectively remove the second region from the metal-containing resist film, the control of (b) including (b1) removing the second region with a first selectivity relative to the first region, and (b2) further removing the second region with a second selectivity different from the first selectivity.

[0042] Hereinafter, each embodiment of the present disclosure will be described in detail with reference to the drawings. In each drawing, the same or similar elements are given the same reference numerals, and duplicated explanations will be omitted. Unless otherwise specified, the positional relationship such as up, down, left, right, etc. will be described based on the positional relationship shown in the drawing. The dimensional ratio of the drawings does not indicate the actual ratio, and the actual ratio is not limited to the illustrated ratio.

[0043] <Example of heat treatment system configuration> 1 is a diagram for explaining an example of the configuration of a heat treatment system. In one embodiment, the heat treatment system includes a heat treatment apparatus 100 and a control unit 200. The heat treatment system is an example of a substrate processing system, and the heat treatment apparatus 100 is an example of a substrate processing apparatus.

[0044] The heat treatment apparatus 100 has a processing chamber 102 configured to be capable of forming a sealed space. The processing chamber 102 is, for example, an airtight cylindrical container, and configured to be capable of adjusting the internal atmosphere. A side wall heater 104 is provided on the side wall of the processing chamber 102. A ceiling heater 130 is provided on the ceiling wall (top plate) of the processing chamber 102. A ceiling surface 140 of the ceiling wall (top plate) of the processing chamber 102 is formed as a horizontal flat surface, and the temperature thereof is adjusted by the ceiling heater 130.

[0045] A substrate support 121 is provided at the lower side in the processing chamber 102. The substrate support 121 has a substrate support surface on which the substrate W is supported. The substrate support 121 is formed, for example, in a circular shape in a plan view, and the substrate W is placed on its horizontally formed surface (upper surface). A stage heater 120 is embedded in the substrate support 121. This stage heater 120 can heat the substrate W placed on the substrate support 121. A ring assembly (not shown) may be disposed in the substrate support 121 so as to surround the substrate W. The ring assembly may include one or more annular members. By disposing the ring assembly around the substrate W, the temperature controllability of the outer peripheral region of the substrate W can be improved. The ring assembly may be made of an inorganic material or an organic material depending on the intended heat treatment.

[0046] The substrate support 121 is supported in the processing chamber 102 by pillars 122 provided on the bottom surface of the processing chamber 102. A plurality of lift pins 123 that can be raised and lowered vertically are provided on the circumferential outer side of the pillars 122. Each of the lift pins 123 is inserted into a through hole provided in the substrate support 121. The lift pins 123 are arranged at intervals in the circumferential direction. The lifting and lowering operation of the lift pins 123 is controlled by a lifting mechanism 124. When the lift pins 123 protrude from the surface of the substrate support 121, the substrate W can be transferred between a transport mechanism (not shown) and the substrate support 121.

[0047] An exhaust port 131 having an opening is provided in a sidewall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump, a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. The pressure inside the processing chamber 102 is adjusted by adjusting the exhaust flow rate, etc. by the exhaust mechanism 132. Note that a transfer port for a substrate W (not shown) is formed in a position different from the position where the exhaust port 131 opens in the sidewall of the processing chamber 102 so as to be freely opened and closed.

[0048] Further, a gas nozzle 141 is provided on the sidewall of the processing chamber 102 at a position different from the exhaust port 131 and the transfer port for the substrate W. The gas nozzle 141 supplies a processing gas into the processing chamber 102. The gas nozzle 141 is provided on the sidewall of the processing chamber 102 on the opposite side to the exhaust port 131 when viewed from the center of the substrate support 121. That is, the gas nozzle 141 is provided on the sidewall of the processing chamber 102 symmetrically to the exhaust port 131 with respect to a vertical imaginary plane that passes through the center of the substrate support 121.

[0049] The gas nozzle 141 is formed in a rod shape protruding from the sidewall of the processing chamber 102 toward the center of the processing chamber 102. The tip of the gas nozzle 141 extends, for example, horizontally from the sidewall of the processing chamber 102. The processing gas is discharged into the processing chamber 102 from a discharge port opening at the tip of the gas nozzle 141, flows in the direction of the dashed-dotted arrow shown in FIG. 1, and is exhausted from the exhaust port 131. The tip of the gas nozzle 141 may have a shape extending obliquely downward toward the substrate W, or may have a shape extending obliquely upward toward the ceiling surface 140 of the processing chamber 102.

[0050] The gas nozzle 141 may be provided, for example, in a ceiling wall of the processing chamber 102. The exhaust port 131 may be provided in a bottom surface of the processing chamber 102.

[0051] The heat treatment apparatus 100 has a gas supply pipe 152 connected to a gas nozzle 141 from the outside of the processing chamber 102. A piping heater 160 for heating the gas in the gas supply pipe 152 is provided around the gas supply pipe 152. The gas supply pipe 152 is connected to a gas supply unit 170. The gas supply unit 170 includes at least one gas source and at least one flow rate controller. The gas supply unit may include a vaporizer that vaporizes a material in a liquid state.

[0052] The control unit 200 processes computer-executable instructions that cause the heat treatment device 100 to perform various steps described in this disclosure. The control unit 200 may be configured to control each element of the heat treatment device 100 to perform various steps described herein. In one embodiment, a part or all of the control unit 200 may be included in the heat treatment device 100. The control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3. The control unit 200 is realized by, for example, a computer 200a. The processing unit 200a1 may be configured to read a program from the storage unit 200a2 and execute the read program to perform various control operations. This program may be stored in the storage unit 200a2 in advance, or may be acquired via a medium when necessary. The acquired program is stored in the storage unit 200a2, and is read from the storage unit 200a2 by the processing unit 200a1 and executed. The medium may be various storage media readable by the computer 200a, or may be a communication line connected to the communication interface 200a3. The processing unit 200a1 may be a central processing unit (CPU). The storage unit 200a2 may include a random access memory (RAM), a read only memory (ROM), a hard disk drive (HDD), a solid state drive (SSD), or a combination of these. The communication interface 200a3 may communicate with the heat treatment device 100 via a communication line such as a local area network (LAN).

[0053] <Example of plasma system configuration> FIG. 2 is a diagram for explaining a configuration example in the case where the plasma processing system is used as a development processing system. In one embodiment, the plasma processing system includes a plasma processing device 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing device 1 is an example of a substrate processing device. The plasma processing device 1 includes a plasma processing chamber (hereinafter, also simply referred to as a "processing chamber") 10, a substrate support unit 11, and a plasma generation unit 12. The plasma processing chamber 10 has a plasma processing space. The plasma processing chamber 10 also has at least one gas supply port for supplying at least one processing gas to the plasma processing space, and at least one gas exhaust port for exhausting gas from the plasma processing space. The gas supply port is connected to a gas supply unit 20 described later, and the gas exhaust port is connected to an exhaust system 40 described later. The substrate support unit 11 is disposed in the plasma processing space, and has a substrate support surface for supporting a substrate.

[0054] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be a capacitively coupled plasma (CCP), an inductively coupled plasma (ICP), an electron-cyclotron-resonance plasma (ECR plasma), a helicon wave plasma (HWP), or a surface wave plasma (SWP), etc. Also, various types of plasma generating units may be used, including an alternating current (AC) plasma generating unit and a direct current (DC) plasma generating unit. In one embodiment, the AC signal (AC power) used in the AC plasma generating unit has a frequency in the range of 100 kHz to 10 GHz. Thus, the AC signal includes a radio frequency (RF) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0055] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various steps described in this disclosure. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to perform the various steps described herein. In one embodiment, a part or all of the control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 is realized by, for example, a computer 2a. The control unit 2 may include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. Each component of the control unit 2 may be similar to each component of the control unit 200 (see FIG. 1) described above.

[0056] The following describes a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1. Fig. 3 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0057] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply 20, a power supply 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support 11 and a gas inlet. The gas inlet is configured to introduce at least one processing gas into the plasma processing chamber 10. The gas inlet includes a showerhead 13. The substrate support 11 is disposed in the plasma processing chamber 10. The showerhead 13 is disposed above the substrate support 11. In one embodiment, the showerhead 13 forms at least a part of a ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the showerhead 13, a sidewall 10a of the plasma processing chamber 10, and the substrate support 11. The plasma processing chamber 10 is grounded. The showerhead 13 and the substrate support 11 are electrically insulated from a housing of the plasma processing chamber 10.

[0058] The substrate support 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central region 111a for supporting the substrate W and an annular region 111b for supporting the ring assembly 112. A wafer is an example of the substrate W. The annular region 111b of the main body 111 surrounds the central region 111a of the main body 111 in a plan view. The substrate W is disposed on the central region 111a of the main body 111, and the ring assembly 112 is disposed on the annular region 111b of the main body 111 so as to surround the substrate W on the central region 111a of the main body 111. Therefore, the central region 111a is also called a substrate support surface for supporting the substrate W, and the annular region 111b is also called a ring support surface for supporting the ring assembly 112.

[0059] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive member. The conductive member of the base 1110 may function as a lower electrode. The electrostatic chuck 1111 is disposed on the base 1110. The electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within the ceramic member 1111a. The ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that other members surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member, may have the annular region 111b. In this case, the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating member, or may be disposed on both the electrostatic chuck 1111 and the annular insulating member. Also, at least one RF / DC electrode coupled to an RF power source 31 and / or a DC power source 32 described later may be disposed in the ceramic member 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or a DC signal described later is supplied to the at least one RF / DC electrode, the RF / DC electrode is also called a bias electrode. Note that the conductive member of the base 1110 and the at least one RF / DC electrode may function as multiple lower electrodes. Also, the electrostatic electrode 1111b may function as a lower electrode. Thus, the substrate support 11 includes at least one lower electrode.

[0060] The ring assembly 112 includes one or more annular members. In one embodiment, the one or more annular members include one or more edge rings and at least one cover ring. The edge rings are formed of a conductive or insulating material, and the cover rings are formed of an insulating material.

[0061] The substrate support 11 may also include a temperature adjustment module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature adjustment module may include a heater, a heat transfer medium, a flow passage 1110a, or a combination thereof. A heat transfer fluid such as a brine or a gas flows through the flow passage 1110a. In one embodiment, the flow passage 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111. The substrate support 11 may also include a heat transfer gas supply configured to supply a heat transfer gas to a gap between the back surface of the substrate W and the central region 111a.

[0062] The shower head 13 is configured to introduce at least one processing gas from the gas supply unit 20 into the plasma processing space 10s. The shower head 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and multiple gas inlets 13c. The processing gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the multiple gas inlets 13c. The shower head 13 also includes at least one upper electrode. Note that the gas introduction unit may include, in addition to the shower head 13, one or more side gas injectors (SGIs) attached to one or more openings formed in the sidewall 10a.

[0063] The gas supply 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply 20 is configured to supply at least one process gas from a respective gas source 21 through a respective flow controller 22 to the showerhead 13. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Additionally, the gas supply 20 may include at least one flow modulation device to modulate or pulse a flow rate of the at least one process gas.

[0064] The power source 30 includes an RF power source 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The RF power source 31 is configured to supply at least one RF signal (RF power) to at least one lower electrode and / or at least one upper electrode. This causes a plasma to be formed from at least one processing gas supplied to the plasma processing space 10s. Thus, the RF power source 31 can function as at least a part of the plasma generating unit 12. In addition, by supplying a bias RF signal to the at least one lower electrode, a bias potential is generated on the substrate W, and ion components in the formed plasma can be attracted to the substrate W.

[0065] In one embodiment, the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b. The first RF generating unit 31a is coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit, and is configured to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generating unit 31a may be configured to generate a plurality of source RF signals having different frequencies. The generated one or more source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0066] The second RF generating unit 31b is coupled to at least one lower electrode via at least one impedance matching circuit and configured to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF generating unit 31b may be configured to generate a plurality of bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. Also, in various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0067] The power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generator 32a and a second DC generator 32b. In one embodiment, the first DC generator 32a is connected to at least one lower electrode and configured to generate a first DC signal. The generated first DC signal is applied to the at least one lower electrode. In one embodiment, the second DC generator 32b is connected to at least one upper electrode and configured to generate a second DC signal. The generated second DC signal is applied to the at least one upper electrode.

[0068] In various embodiments, the first and second DC signals may be pulsed. In this case, a sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulses may have a rectangular, trapezoidal, triangular or combination of these pulse waveforms. In one embodiment, a waveform generator for generating a sequence of voltage pulses from the DC signal is connected between the first DC generator 32a and at least one lower electrode. Thus, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. When the second DC generator 32b and the waveform generator constitute a voltage pulse generator, the voltage pulse generator is connected to at least one upper electrode. The voltage pulses may have a positive polarity or a negative polarity. Also, the sequence of voltage pulses may include one or more positive polarity voltage pulses and one or more negative polarity voltage pulses in one period. The first and second DC generating units 32a, 32b may be provided in addition to the RF power supply 31, or the first DC generating unit 32a may be provided in place of the second RF generating unit 31b.

[0069] The exhaust system 40 may be connected to, for example, a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure in the plasma processing space 10s is adjusted by the pressure regulating valve. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0070] <Example of liquid processing system configuration> 4 is a diagram for explaining an example of the configuration of a liquid processing system. In one embodiment, the liquid processing system includes a liquid processing apparatus 300 and a control unit 400. The liquid processing system is an example of a substrate processing system, and the liquid processing apparatus 300 is an example of a substrate processing apparatus.

[0071] 4, liquid processing apparatus 300 has spin chuck 311 as a substrate support section in processing chamber 310. Spin chuck 311 holds substrate W horizontally. Spin chuck 311 is connected to a rotating section 312 that can be raised and lowered, and rotating section 312 is connected to a rotation drive section 313 constituted by a motor or the like. Substrate W held by spin chuck 311 can be rotated by driving rotation drive section 313.

[0072] A cup 321 is disposed outside the spin chuck 311 to prevent processing liquid (resist liquid, developer, cleaning liquid, etc.) and mist of the processing liquid from scattering around the cup 321. A drain pipe 323 and an exhaust pipe 324 are provided at a bottom 322 of the cup 321. The drain pipe 323 is connected to a drainage device 325 such as a drainage pump. The exhaust pipe 324 is connected via a valve 326 to an exhaust device 327 such as an exhaust pump.

[0073] An air blower 314 is provided at the upper part of processing chamber 310 of liquid processing apparatus 300, for supplying air at a required temperature and humidity as a downflow into cup 321.

[0074] A processing liquid supply nozzle 331 is used when forming a puddle of processing liquid on the substrate W. This processing liquid supply nozzle 331 is provided on a nozzle support portion 332, such as an arm, and the nozzle support portion 332 can be moved up and down by a drive mechanism as indicated by a reciprocating arrow A shown by a dashed line in the figure, and can also be moved horizontally as indicated by a reciprocating arrow B shown by a dashed line. A processing liquid (resist liquid, developer, etc.) is supplied to the processing liquid supply nozzle 331 from a processing liquid supply source 334 via a supply pipe 333.

[0075] When forming a paddle, if a so-called long nozzle having a discharge port having a length equal to or greater than the diameter of the substrate W is used, a paddle of the processing liquid can be formed on the substrate W by scanning from one end to the other end of the substrate W. In the case of a so-called straight type nozzle that discharges liquid to form a liquid column having a width sufficiently smaller than the diameter of the substrate W, the discharge port is positioned above the center of the substrate W, and the processing liquid is discharged while rotating the substrate W, thereby spreading the processing liquid over the entire surface of the substrate W and forming a paddle of the processing liquid on the substrate W. In addition, the paddle of the processing liquid may be formed by scanning a straight type nozzle over the substrate W in the same manner as the long nozzle, or by arranging multiple discharge ports for discharging liquid like the straight type nozzle over the substrate W and supplying the processing liquid from each of the discharge ports.

[0076] Gas nozzle 341 has nozzle body 342. Nozzle body 342 is provided on a nozzle support such as an arm, and the nozzle support can be moved up and down by a drive mechanism as indicated by a reciprocating arrow C shown by a dashed line in the figure, and can also be moved horizontally as indicated by a reciprocating arrow D shown by a dashed line.

[0077] The gas nozzle 341 has two nozzle outlets 343 and 344. The nozzle outlets 343 and 344 are formed by branching off from a gas flow path 345. The gas flow path 345 is connected to a gas supply source 347 via a gas supply pipe 346. In the gas supply source 347, an inert gas or a non-oxidizing gas, such as nitrogen gas, is prepared. When nitrogen gas, for example, is supplied from the gas flow path 345 to the gas nozzle 341, the nitrogen gas is discharged from each of the nozzle outlets 343 and 344.

[0078] Further, the gas nozzle 341 is provided with a cleaning liquid supply nozzle 351 for cleaning the substrate W with the processing liquid after liquid processing. The cleaning liquid supply nozzle 351 is connected to a cleaning liquid supply source 353 via a cleaning liquid supply pipe 352. For example, pure water is used as the cleaning liquid. The cleaning liquid supply nozzle 351 is positioned between the two nozzle outlets 343 and 344 described above, but the position is not limited thereto. The cleaning liquid supply nozzle 351 may be configured independent of the gas nozzle 341.

[0079] The control unit 400 processes computer-executable instructions that cause the liquid treatment device 300 to perform various steps described in this disclosure. The control unit 400 may be configured to control each element of the liquid treatment device 300 to perform various steps described herein. In one embodiment, a part or all of the control unit 400 may be included in the liquid treatment device 300. The control unit 400 is realized by, for example, a computer 400a. The computer 400a may include a processing unit 400a1, a storage unit 400a2, and a communication interface 400a3. Each component of the control unit 400 may be similar to each component of the control unit 200 (see FIG. 1) described above.

[0080] <First embodiment of substrate processing method> FIG. 5 is a flowchart showing a substrate processing method according to an illustrative first embodiment (hereinafter also referred to as the "first method"). As shown in FIG. 5, the first method includes a step ST11 of providing a substrate and a step ST12 of developing the substrate. In one embodiment, the development process in step ST12 is performed by a dry process using a processing gas (hereinafter also referred to as the "dry development"). In one embodiment, the development process in step ST12 is performed by a wet process using a developer (hereinafter also referred to as the "wet development"). In one embodiment, the development process in step ST12 is performed by using both wet development and dry development.

[0081] The first method may be performed using any one of the above-mentioned substrate processing systems (see FIGS. 1 to 4), or may be performed using two or more of these substrate processing systems. For example, the first method may be performed in a heat treatment system (see FIG. 1). In the following, an example will be described in which the control unit 200 controls each part of the heat treatment apparatus 100 to perform the first method on the substrate W.

[0082] (Step ST11: Providing the substrate) First, in step ST11, the substrate W is provided in the processing chamber 102 of the heat treatment apparatus 100. The substrate W is provided on the substrate support 121 via the lift pins 123. After the substrate W is placed on the substrate support 121, the temperature of the substrate support 121 is adjusted to a set temperature. The temperature of the substrate support 121 may be adjusted by controlling the output of one or more heaters among the sidewall heater 104, the stage heater 120, the ceiling heater 130, and the piping heater 160 (hereinafter collectively referred to as "each heater"). In this processing method, the temperature of the substrate support 121 may be adjusted to a set temperature before step ST11. That is, the substrate W may be provided on the substrate support 121 after the temperature of the substrate support 121 is adjusted to the set temperature.

[0083] 6 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11. The substrate W includes an undercoat film UF and a resist film RM formed on the undercoat film UF. The substrate W may be used for manufacturing semiconductor devices. The semiconductor devices include, for example, memory devices such as DRAM and 3D-NAND flash memory, and logic devices.

[0084] The resist film RM is a metal-containing resist film that contains a metal. In one example, the metal may include at least one metal selected from the group consisting of Sn, Hf, and Ti. In one example, the resist film RM contains Sn and may include tin oxide (SnO) and tin hydroxide (Sn-OH bond). The resist film RM may further include an organic substance.

[0085] 6, the resist film RM has an exposed first region RM1 and an unexposed second region RM2. The first region RM1 is an area exposed to EUV light, i.e., an EUV-exposed region. The second region RM2 is an area not exposed to EUV light, i.e., an unexposed region. The film thickness of the first region RM1 may be smaller than the film thickness of the second region RM2.

[0086] The undercoat film UF may be an organic film, a dielectric film, a metal film, a semiconductor film, or a laminated film thereof formed on a silicon wafer. In one embodiment, the undercoat film UF includes at least one selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film.

[0087] 7 and 8 are diagrams showing an example of an undercoat film UF of a substrate W. As shown in Fig. 7, the undercoat film UF may be composed of a first film UF1, a second film UF2, and a third film UF3. As shown in Fig. 8, the undercoat film UF may be composed of a second film UF2 and a third film UF3.

[0088] The first film UF1 is, for example, a spin-on-glass (SOG) film, a SiC film, a SiON film, a Si-containing anti-reflective film (SiARC), or an organic film. The second film UF2 is, for example, a spin-on-carbon (SOC) film, an amorphous carbon film, or a silicon-containing film. The third film UF3 is, for example, a silicon-containing film. The silicon-containing film is, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbonitride film, a polycrystalline silicon film, or a carbon-containing silicon film. The third film UF3 may be composed of a plurality of stacked silicon-containing films. For example, the third film UF3 may be composed of a silicon oxide film and a silicon nitride film that are alternately stacked. The third film UF3 may also be composed of a silicon oxide film and a polycrystalline silicon film that are alternately stacked. The third film UF3 may also be a stacked film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. The third film UF3 may also be composed of a silicon oxide film and a silicon carbonitride film that are stacked. The third film UF3 may be a laminated film including a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.

[0089] In one embodiment, the substrate W is formed as follows. First, a photoresist film containing a metal is formed on an undercoat film that has been subjected to adhesion treatment or the like. The film formation may be performed by a dry process, a wet process such as a solution coating method, or both a dry process and a wet process. Before the photoresist film is formed, a surface modification process of the undercoat film may be performed. The substrate after the photoresist film is formed is subjected to a heating process, i.e., a pre-bake (Post Apply Bake: PAB). The substrate after the pre-bake may be subjected to an additional heating process. The wafer after the heating process is transported to an exposure device, and the photoresist film is irradiated with EUV light through an exposure mask (reticle). This forms a substrate W including an undercoat film UF and a resist film RM having an exposed first region RM1 and an unexposed second region RM2. The first region RM1 is a region corresponding to an opening provided in the exposure mask (reticle). The second region RM2 is a region corresponding to a pattern provided in the exposure mask (reticle). The EUV light has a wavelength in the range of, for example, 10 to 20 nm. The EUV light may have a wavelength in the range of 11 to 14 nm, and in one example has a wavelength of 13.5 nm. The exposed substrate is transported from the exposure tool to a heat treatment tool under atmosphere control and undergoes a heat treatment, i.e., a post-exposure bake (PEB). The substrate W after the PEB may be subjected to an additional heat treatment.

[0090] In the first region RM1 exposed to EUV, there may be a portion where the exposure reaction is weak along the thickness direction of the resist film RM (the direction of arrow D in Figures 6 to 8, hereinafter also referred to as the "depth direction"). This is thought to be due to stochastic fluctuations in the EUV photon distribution and a shallow depth of focus. In the example shown in Figures 6 to 8, the first region RM1 has, along the thickness direction, a first portion RM1a and a second portion RM1b which has a weaker exposure reaction than the first portion RM1a. The second portion RM1b is a portion of the first region RM1 that contacts the underlayer UF.

[0091] The second portion RM1b has a weak exposure reaction, and therefore has film properties similar to those of the second region RM2, which is an unexposed region. Therefore, in the resist film RM shown in Figures 6 to 8, it is difficult to obtain a development contrast (the ratio of the development speed of the exposed region to the unexposed region) along the thickness direction. If the resist film RM is developed under the same conditions along the thickness direction, the side surface below the first region RM1 (second portion RM1b) becomes more likely to be removed together with the second region RM2 as the development progresses.

[0092] FIG. 9 is a diagram showing an example of the cross-sectional structure of the substrate W after development. FIG. 9 shows an example of the case where the substrate W shown in FIG. 6 is developed under the same conditions along the thickness direction. In the example shown in FIG. 9, the first region RM after development has a cross-sectional dimension of the second portion RM1b that is smaller along the thickness direction, and has an inverse tapered shape. It is considered that the second portion RM1b of the first region RM1 has a smaller development contrast with respect to the second region RM2 along the thickness direction compared to the first portion RM1a, and is easily removed by development together with the second region RM2. For this reason, the first method develops the step ST121 and the step ST122 under different conditions. For example, the first method develops the step ST121 and the step ST122 with different development contrasts. Thereby, even if the intensity of the exposure reaction differs in the thickness direction in the resist film RM, the shape of the developed pattern can be adjusted, and deterioration of the pattern shape and roughness can be suppressed.

[0093] (Step ST12: Developing the substrate) Next, in step ST12, the resist film RM of the substrate W is developed, and the second region RM2 is selectively removed. Step ST12 includes step ST120 of developing the substrate with a first selectivity and step ST122 of developing the substrate with a second selectivity different from the first selectivity.

[0094] (Step ST120: Development with a first selection ratio) First, in step ST120, a first process gas containing a first developing gas is supplied into the process chamber 102 through the gas nozzle 141. In one embodiment, the first developing gas contains a halogen-containing gas. The halogen-containing gas may be a gas containing a halogen-containing inorganic acid, and may be a gas containing Br or Cl. The gas containing a halogen-containing inorganic acid may be a gas containing a hydrogen halide and / or a boron halide. The gas containing a halogen-containing inorganic acid may be, for example, HBr gas, BCl gas, or the like. 3 The first developing gas is at least one selected from the group consisting of a carboxylic acid, a β-dicarbonyl compound, and an alcohol. In one embodiment, the first developing gas is a gas containing an organic acid. The gas containing an organic acid may be, for example, a gas containing at least one selected from the group consisting of a carboxylic acid, a β-dicarbonyl compound, and an alcohol. In one embodiment, the first developing gas is a gas containing a carboxylic acid. Examples of the carboxylic acid include formic acid (HCOOH), acetic acid (CH 3 COOH), trichloroacetic acid (CCl 3 COOH), monofluoroacetic acid (CFH 2 COOH), difluoroacetic acid (CF2FCOOH), trifluoroacetic acid (CF 3 COOH) chloro-difluoroacetic acid (CClF 2 COOH), sulfur-containing acetic acid, thioacetic acid (CH 3 COSH, thioglycolic acid (HSCH 2 COOH), trifluoroacetic anhydride ((CF 3 CO) 2 O), acetic anhydride ((CH 3 CO) 2 In one embodiment, the first developing gas includes a β-dicarbonyl compound. The β-dicarbonyl compound is, for example, acetylacetone (CH 3 C(O)CH 2 C(O)CH 3 ), trichloroacetylacetone (CCl 3 C(O)CH 2 C(O)CH 3 ), hexachloroacetylacetone (CCl 3 C(O)CH 2 C(O)CCl3 ), trifluoroacetylacetone (CF 3 C(O)CH 2 C(O)CH 3 ), hexafluoroacetylacetone (HFAc, CF 3 C(O)CH 2 C(O)CF 3 In one embodiment, the first developing gas includes an alcohol. The alcohol, in one example, is nonafluoro-tert-butyl alcohol (CF 3 ) 3 C-OH) is fine.

[0095] In one embodiment, the first developing gas is a gas containing trifluoroacetic acid. In one embodiment, the first developing gas contains a halogenated organic acid vapor. In one embodiment, the first developing gas is trifluoroacetic anhydride, acetic anhydride, trichloroacetic acid, CFH 2 COOH, CF 2 The first developing gas includes at least one selected from the group consisting of HCOOH, chlorodifluoroacetic acid, sulfur-containing acetic acid, thioacetic acid, and thioglycolic acid. In one embodiment, the first developing gas is a mixed gas of carboxylic acid and hydrogen halide or a mixed gas of acetic acid and formic acid. In one embodiment, the first processing gas is a gas containing acetic acid.

[0096] In step ST120, the second region RM2 of the resist film RM is removed with a first selectivity relative to the first region RM1. In the first method, the "selectivity" is also called development contrast, and is the ratio of the development rate of the second region RM2 to the development rate of the first region RM1. The first selectivity may be appropriately set within a range in which the second region RM2 is selectively removed relative to the first region RM1 (i.e., a value greater than 1). The first selectivity may be set relatively low to such an extent that a part of the first region RM1 is removed. In this case, even if there is a portion that has been exposed to EUV light other than the first region RM1 (a portion corresponding to the opening of the exposure mask), the resist film in that portion can be removed, and the portion can be prevented from remaining as a residue.

[0097] Step ST120 may be performed until the second region RM2 is removed to a given depth or until an opening formed by development has a given aspect ratio. The given depth or aspect ratio may be set based on the progress of the exposure reaction of the first region RM1 (based on the thickness of the first portion RM1a or the second portion RM1b, for example). In one embodiment, step ST120 may be performed until just before the second portion RM1b of the first region RM1 is exposed or until it is partially exposed.

[0098] Fig. 10 is a diagram showing an example of a cross-sectional structure of the substrate W after processing in step ST120. In the example shown in Fig. 10, the second region RM2 of the resist film RM is selectively removed with respect to the first region RM1, and the side surface of the first portion RM1a of the first region is exposed (the second portion RM1b is not exposed at this stage).

[0099] (Step ST122: Development with the second selection ratio) In step ST122, a second process gas containing a second developing gas is supplied into the process chamber 102 through the gas nozzle 141. The second developing gas may be the same as or different from that in step ST120.

[0100] In step ST122, the second region RM2 of the resist film RM is removed with respect to the first region at a second selectivity ratio different from the first selectivity ratio. The selectivity ratio may be made different from the first selectivity by changing, from step ST120, one or more of the development conditions, such as the set temperature of the substrate W or the substrate support 11, the pressure in the processing chamber 102, and the type and concentration (partial pressure) of the processing gas.

[0101] In one embodiment, the second selectivity is higher than the first selectivity. For example, in step ST122, the second selectivity may be made higher than the first selectivity by performing any one or more of the following (I) to (IV).

[0102] (I) In step ST122, the set temperature of the substrate W or the substrate support part 121 is set lower than that in step ST120. For example, when HBr gas is used as the second developing gas, the set temperature of the substrate support part 121 in step ST120 may be set to 20° C. or higher and 60° C. or lower, or 40° C. or higher and 60° C. or lower, and the set temperature of the substrate support part 121 in step ST122 may be set to −20° C. or higher and lower than 20° C. For example, when BCl gas is used as the second developing gas, 3 When gas is used, the set temperature of the substrate supporting part 121 in step ST120 may be 120° C. or more and 180° C. or less, and the set temperature of the substrate supporting part 121 in step ST122 may be 60° C. or more and less than 120° C.

[0103] (II) In step ST122, the pressure in the processing chamber 102 is set lower than that in step ST120. For example, when HBr gas is used as the second developing gas, the pressure in the chamber 102 in step ST120 may be set to 1 Torr or more and 10 Torr or less, and the pressure in the processing chamber 102 in step ST122 may be set to 0.01 Torr or more and 1 Torr or less.

[0104] (III) In step ST122, the acidity of the second developing gas is made lower than that of the first developing gas. That is, in step ST122, a second developing gas having a larger acid dissociation constant (pKa) than the first developing gas used in step ST120 is used. For example, the developing gas may be changed from a gas containing a halogen-containing inorganic acid (step ST120) to a gas containing an organic acid (step ST122). In one example, the developing gas is changed to HBr gas or BCl gas. 3 The developing gas may be changed from a gas containing a halogen-containing inorganic acid with high acidity (step ST120) to a gas containing a halogen-containing inorganic acid with low acidity (step ST122), or from a gas containing an organic acid with high acidity (step ST120) to a gas containing an organic acid with low acidity (step ST122). In one example, the developing gas may be changed from HBr gas (step ST120) to BCl 3gas (step ST122). Also, for example, when a mixed gas is used as the developing gas, the flow rate (partial pressure) of "a gas having a relatively large acid dissociation constant (pKa)" in the mixed gas may be increased in the second developing gas compared to the first developing gas. For example, when the first developing gas and the second developing gas in steps ST120 and 122 are mixed gases of HBr gas and carboxylic acid gas, respectively, the flow rate (partial pressure) of the carboxylic acid gas in the second developing gas may be increased compared to the flow rate (partial pressure) of the carboxylic acid gas in the first developing gas.

[0105] (IV) In step ST122, the concentration (partial pressure) of the developing gas in the processing gas is set lower than the concentration (partial pressure) of the developing gas in the processing gas in step ST120. For example, when a mixed gas containing the developing gas and a noble gas such as Ar is used as the processing gas, the concentration (partial pressure) of the developing gas in step ST122 is set lower than the concentration (partial pressure) of the developing gas in step ST120.

[0106] Step ST122 may be performed until the second region RM2 is removed and the base film UF is exposed. Step ST122 may be performed until the base film UF is partially removed (over-etched) in the depth direction.

[0107] FIG. 11 is a diagram showing an example of a cross-sectional structure of the substrate W after the process of step ST122. In the example shown in FIG. 11, the second region RM2 of the resist film RM is removed to form an opening OP. The opening OP is defined by the side surface of the first region RM1. The opening OP is a space on the undercoat film UF surrounded by the side surface. The opening OP has a shape corresponding to the second region RM2 in a plan view of the substrate W (a shape corresponding to an exposure mask pattern used for EUV exposure). The shape may be, for example, a circle, an ellipse, a rectangle, a line, or a combination of one or more of these shapes. A plurality of openings OP may be formed in the resist film RM. Each of the plurality of openings OP may have a linear shape and may be arranged at regular intervals to form a line-and-space pattern. A plurality of openings OP may also be arranged in a lattice pattern to form a pillar pattern.

[0108] As described above, the first method includes a step ST120 of developing with a first selectivity and a step ST122 of developing with a second selectivity different from the first selectivity. This allows the shape of the developed pattern to be adjusted. Even if the intensity of the exposure reaction differs in the thickness direction in the resist film RM, the second region RM2 can be removed with an appropriate selectivity relative to the first region RM1, and deterioration of the pattern shape and roughness can be suppressed.

[0109] Fig. 12 is a flowchart according to a modified example of the first method. As shown in Fig. 12, step ST12 may include step ST121 of modifying the resist film between step ST120 and step ST122.

[0110] In step ST121, a modification process is performed on the resist film RM. In one embodiment, the modification process is performed by heating the substrate W. The heating process of the substrate W may be performed, for example, by controlling the output of one or more of the heaters of the heat treatment apparatus 100 to adjust the temperature of the substrate support portion 121. The substrate W may be heated to, for example, 180° C. or higher. The substrate W may be heated to, for example, a temperature of 190° C. or higher and 240° C. or lower. The substrate W may be heated to, for example, a temperature of 190° C. or higher and 220° C. The chamber in which the substrate W is heated is filled with air, N 2 Gas and / or H 2 The atmosphere may contain O gas. The modification process increases the metal film density in the first region RM1, and the development resistance can be improved. Since the second region RM2 is partially removed in step ST121 (see FIG. 10), the modification also easily progresses to the portion RM1b of the first region RM1 that is less sensitive to exposure. This can suppress a decrease in the development contrast along the depth direction of the resist film RM.

[0111] The heat treatment in step ST121 may be performed in a processing chamber 102 of a heat treatment apparatus 100 different from that in which steps ST120 and ST122 are performed. The heat treatment in step ST121 may be performed using an apparatus different from the heat treatment apparatus 100. For example, the substrate W may be heated by irradiating the substrate W with electromagnetic waves using an apparatus that generates electromagnetic waves such as infrared light or microwaves.

[0112] In one embodiment, the modification process in step ST121 is performed by plasma processing. The plasma processing may be performed, for example, by transporting the substrate W from the heat treatment device 100 to the plasma treatment device 1 and exposing the substrate W to plasma generated in the plasma treatment device 1. The plasma processing may be performed, for example, by introducing a process gas excited by a remote plasma source into the process chamber 102 of the heat treatment device 100. The process gas for generating plasma may be an inert gas. For example, the inert gas is a noble gas such as He, Ar, Ne, Kr, or Xe, or nitrogen gas.

[0113] In one embodiment, the first method may be performed using a plasma processing system (see FIG. 2 and FIG. 3). For example, a substrate W may be provided on a substrate support 11 in a processing chamber 10 of a plasma processing apparatus 1 (step ST11), and a processing gas may be supplied from a gas supply unit 20 into the processing chamber 10 to perform dry development of the resist film RM (step ST12). The processing gas may be the same as that used in the case of using a thermal processing system. In step ST120 and / or step ST122, a source RF signal may be supplied to the lower electrode of the substrate support 11 and / or the upper electrode of the shower head 13. A bias signal may also be supplied to the lower electrode of the substrate support 11. In this case, plasma is generated from the processing gas in the chamber 10, and active species such as ions and radicals in the plasma are attracted to the substrate W, which may promote development.

[0114] When a plasma processing system is used, development may be performed with a second selectivity ratio different from the first selectivity ratio in step ST122 by changing one or more of the development conditions from step ST120. The development conditions to be changed include, for example, the set temperature of the substrate W or the substrate support 11, the pressure in the processing chamber 10, the type and concentration (partial pressure) of the processing gas, the power level of the source RF signal, and the power level or voltage level of the bias signal.

[0115] When a plasma processing system is used, the second selectivity may be made higher than the first selectivity in step ST122 by performing, for example, any one or more of the following (I) to (IV).

[0116] (I) In step ST122, the set temperature of the substrate W or the substrate support 11 is set lower than that in step ST120. For example, when HBr gas is used as the processing gas, the set temperature of the substrate support 11 in step ST120 may be set to 20° C. or higher and 60° C. or lower, or 40° C. or higher and 60° C. or lower, and the set temperature of the substrate support 11 in step ST122 may be set to -20° C. or higher and lower than 20° C. For example, when BCl gas is used as the processing gas, 3 When gas is used, the set temperature of the substrate support part 11 in step ST120 may be set to 120° C. or more and 180° C. or less, and the set temperature of the substrate support part 121 in step ST122 may be set to 60° C. or more and less than 120° C. The substrate support part 11 may be adjusted to the set temperature by a temperature adjustment module. The substrate support part 11 may also be adjusted to the set temperature by controlling the pressure of a heat transfer gas (e.g., He) between the electrostatic chuck 1111 and the rear surface of the substrate W.

[0117] (II) In step ST122, the pressure in the processing chamber 10 is set lower than that in step ST120. For example, the pressure in the processing chamber 10 in step ST120 may be set to 1 Torr or more and 10 Torr or less, and the pressure in the processing chamber 10 in step ST122 may be set to 0.01 Torr or more and 1 Torr or less.

[0118] (III) In step ST122, the acidity of the second developing gas is made lower than that of the first developing gas. That is, in step ST122, a second developing gas having a larger acid dissociation constant (pKa) than the first developing gas used in step ST120 is used. For example, the developing gas may be changed from a gas containing a halogen-containing inorganic acid (step ST120) to a gas containing an organic acid (step ST122). In one example, the developing gas is changed to HBr gas or BCl gas. 3 The developing gas may be changed from a gas containing a halogen-containing inorganic acid having a high acidity (step ST120) to a gas containing a halogen-containing inorganic acid having a low acidity (step ST122), or from a gas containing an organic acid having a high acidity (step ST120) to a gas containing an organic acid having a low acidity (step ST122). In one example, the developing gas may be changed from HBr gas (step ST120) to BCl 3 gas (step ST122). Also, for example, when a mixed gas is used as the developing gas, the flow rate (partial pressure) of "a gas having a relatively large acid dissociation constant (pKa)" in the mixed gas may be increased in the second developing gas compared to the first developing gas. For example, when the first developing gas and the second developing gas in steps ST120 and 122 are mixed gases of HBr gas and carboxylic acid gas, respectively, the flow rate (partial pressure) of the carboxylic acid gas in the second developing gas may be increased compared to the flow rate (partial pressure) of the carboxylic acid gas in the first developing gas.

[0119] (IV) In step ST122, the concentration (partial pressure) of the developing gas in the processing gas is set lower than the concentration (partial pressure) of the developing gas in the processing gas in step ST120. For example, when a mixed gas containing the developing gas and a noble gas such as Ar is used as the processing gas, the concentration (partial pressure) of the developing gas in step ST122 is set lower than the concentration (partial pressure) of the developing gas in step ST120.

[0120] When plasma is generated from the processing gas in steps ST120 and ST122, at least one of the following (V) and (VI) may be performed in addition to or instead of the above (I) to (IV), thereby making the second selectivity higher than the first selectivity.

[0121] (V) In step ST122, the power level of the source RF signal supplied to the chamber 10 is made smaller than the power level of the source RF signal in step ST120.

[0122] (VI) In step ST122, the power or voltage level of the bias signal supplied to the chamber 10 is made smaller than the power or voltage level of the bias signal in step ST120.

[0123] In addition, when the substrate W is dry-developed using a thermal processing system or a plasma processing system, the first method may include a desorption step. The desorption step includes removing scum from the surface of the resist film RM or smoothing the surface of the resist film RM by using an inert gas such as helium or a plasma of the inert gas. The desorption step may be performed after step ST12. The desorption step may be repeated one or more times between step ST120 and step ST122. Moreover, the desorption step may be performed before step ST12 (step ST122) and a step of etching the undercoat film UF described later, instead of between step ST120 and step ST122, or in addition to between step ST120 and step ST122.

[0124] In one embodiment, the first method may be performed in a liquid processing system (see FIG. 4). That is, a substrate may be provided on a spin chuck 311 in a processing chamber 310 of a liquid processing apparatus 300 (step ST11), and a developer may be supplied to the substrate W from a processing liquid supply nozzle 331 to perform wet development of the resist film RM (step ST12). The developer may include, for example, an aromatic compound such as benzene, xylene, or toluene; an ester such as propylene glycol monomethyl ester acetate, ethyl acetate, ethyl lactate, n-butyl acetate, or butyrolactone; an alcohol such as 4-methyl-2-pentanol, 1-butanol, isopropanol, 1-propanol, or methanol; a ketone such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, or 2-octanone; or an ether such as tetrahydrofuran, dioxane, or anisole.

[0125] When a liquid processing system is used, in step ST122, development may be performed with a second selectivity different from the first selectivity by changing, for example, one or more of the solubility, concentration, and temperature of the developer from step ST120.

[0126] When the liquid processing system is used, in step ST122, the second selectivity may be made higher than the first selectivity by performing, for example, any one or more of the following (I) to (III).

[0127] (I) The solubility of the resist film RM in the developer used in step ST122 is made lower than the solubility of the resist film in the developer used in step ST120.

[0128] (II) The concentration of the developer used in step ST122 is made lower than that of the developer used in step ST120, for example, by increasing the dilution degree of the developer.

[0129] (III) The temperature of the developer used in step ST122 is set lower than the temperature of the developer used in step ST120. For example, the temperature of the developer may be controlled to 30° C. or higher and 90° C. or lower in step ST120, and the temperature of the developer may be controlled to 10° C. or higher and 60° C. or lower in step ST122.

[0130] In one embodiment, the development process in step ST12 may be performed by both dry development and wet development. For example, step ST120 may be performed by wet development using a liquid processing system (see FIG. 4), and step ST122 may be performed by dry development using a heat processing system (see FIG. 1) or a plasma processing system (see FIGS. 2 and 3). When wet development is performed before dry development, contamination caused by seepage of the developer into the undercoat film UF and pattern collapse of the resist film caused by the surface tension of the developer can be suppressed. Note that step ST120 may be performed by dry development, and step ST122 may be performed by wet development.

[0131] In one embodiment, the development process in step ST12 may be performed by both a heat treatment and a plasma treatment. For example, step ST120 may be performed by a heat treatment and step ST122 may be performed by a plasma treatment, or step ST120 may be performed by a plasma treatment and step ST122 may be performed by a heat treatment.

[0132] In one embodiment, in step ST12, a cycle including step ST120 and step ST122 may be repeated multiple times. In this case, the cycle of step ST120 and step ST122 may be repeated multiple times by only dry development, or may be repeated multiple times by only wet development. In addition, after performing the cycle of step ST120 and step ST122 by wet development once or more, the cycle of step ST120 and step ST122 may be performed by dry development once or more. In addition, the cycle of step ST120 performed by wet development and step ST122 performed by dry development may be repeated multiple times. Note that, as described above, when the cycle of step ST120 and step ST122 is repeated multiple times, the development conditions of step ST120 and / or step ST122 may be different between one or more cycles and one or more other cycles. For example, the temperature of the substrate support in step ST120 may be lower in one or more cycles for developing to a second depth that is deeper than the first depth than in one or more cycles for developing to a first depth.

[0133] In one embodiment, after step ST12, the base film UF is etched. The etching process may be performed, for example, by generating plasma from a processing gas in the processing chamber 10 of the plasma processing device 1. In the etching process, the resist film RM functions as a mask, and a recess is formed in the base film UF based on the shape of the opening OP. When development is performed using the plasma processing device 1 in step ST12, the etching process may be performed continuously in the same processing chamber 10 as step ST12, or may be performed in a processing chamber 10 of another plasma processing device 1.

[0134] <Second embodiment of substrate processing method> 13 is a flowchart showing a substrate processing method according to an exemplary second embodiment (hereinafter also referred to as a "second method"). As shown in FIG 13, the second method includes a step ST21 of providing a substrate and a step ST22 of developing the substrate.

[0135] In one embodiment, the development process in step ST22 is performed by dry development. In one embodiment, the development process in step ST22 is performed by wet development. In one embodiment, the development process in step ST22 is performed using both wet development and dry development.

[0136] The second method may be performed in the above-mentioned heat treatment system (FIG. 1). In the following, an example will be described in which the control unit 200 controls each unit of the heat treatment apparatus 100 to perform the second method on the substrate W. The second method may be performed by combining the heat treatment system (FIG. 1) with another substrate treatment system such as a plasma treatment system (FIGS. 2 and 3) or a liquid treatment system (FIG. 4).

[0137] (Step ST21: Providing a substrate) First, in step ST21, the substrate W is provided in the processing chamber 102 of the thermal processing apparatus 100. Step ST21 is similar to step ST11 of the first method, and the configuration of the substrate W may be similar to the configuration shown in FIG.

[0138] (Step ST22: Developing the substrate) Next, in step ST22, the resist film RM of the substrate W is developed to selectively remove the first region RM1. The step ST22 includes a step ST220 of developing the substrate with a first selectivity and a step ST222 of developing the substrate with a second selectivity different from the first selectivity.

[0139] (Step ST220: Development with a first selection ratio) First, in step ST220, a process gas containing a developing gas is supplied into the process chamber 102 via the gas nozzle 141. Unlike step ST120 of the first method described above, the developing gas may be a gas capable of selectively removing the first region relative to the second region. This allows the first region RM1 of the resist film RM to be selectively removed relative to the second region RM2.

[0140] In step ST220, the first region RM1 of the resist film RM is removed with a first selectivity relative to the second region RM2. In the second method, the "selectivity" is also called development contrast, and is the ratio of the development rate of the first region RM1 to the development rate of the second region RM2. The first selectivity may be set appropriately within a range in which the first region RM1 is selectively removed relative to the second region RM2 (i.e., a value greater than 1).

[0141] Step ST220 may be performed until the first region RM1 is removed to a given depth, or until an opening formed by development has a given aspect ratio. The given depth or aspect ratio may be set based on the progress of the exposure reaction of the first region RM (based on the thicknesses of the first portion RM1a and the second portion RM1b, for example). In one embodiment, step ST220 may be performed until just before the second portion RM1b of the first region RM1 is removed, or until it is partially removed.

[0142] Fig. 14 is a diagram showing an example of a cross-sectional structure of the substrate W after processing in step ST220. In the example shown in Fig. 14, the first region RM1 of the resist film RM is selectively removed with respect to the second region RM2, and the upper surface of the second portion RM1b of the first region is exposed.

[0143] (Step ST222: Development with second selection ratio) In step ST222, a process gas containing a developing gas is supplied into the process chamber 102 through the gas nozzle 141. The developing gas may be the same as or different from the developing gas used in step ST220. As a result, the first region RM1 of the resist film RM is selectively etched relative to the second region RM2.

[0144] In step ST222, the first region RM1 of the resist film RM is removed with respect to the second region RM2 at a second selectivity ratio different from the first selectivity ratio. The selectivity ratio may be made different from the first selectivity ratio by changing, from step ST220, one or more of the development conditions, such as the set temperature of the substrate W or the substrate support 11, the pressure in the processing chamber 102, and the type and concentration (partial pressure) of the processing gas.

[0145] In one embodiment, the second selectivity is higher than the first selectivity. For example, in step ST122, the second selectivity may be made higher than the first selectivity by performing any one or more of the following (I) to (IV).

[0146] (I) In step ST222, the set temperature of the substrate W or the substrate support 121 is set lower than that in step ST220.

[0147] (II) In step ST222, the pressure in the processing chamber 102 is made higher than that in step ST220.

[0148] (III) In step ST222, the acidity of the developing gas is made greater than the acidity of the developing gas in step ST220.

[0149] (IV) In step ST222, the concentration (partial pressure) of the developing gas in the processing gas is made higher than the concentration (partial pressure) of the developing gas in the processing gas in step ST220.

[0150] Step ST222 may be performed until the first region RM1 is removed and the base film UF is exposed. Step ST222 may be performed until the base film UF is partially removed (over-etched) in the depth direction.

[0151] FIG. 15 is a diagram showing an example of a cross-sectional structure of the substrate W after the process of step ST222. In the example shown in FIG. 15, the first region RM1 of the resist film RM is removed to form an opening OP. The opening OP is defined by the side surface of the second region RM2. The opening OP is a space on the undercoat film UF surrounded by the side surface. The opening OP has a shape corresponding to the first region RM1 in a plan view of the substrate W (a shape corresponding to an opening of an exposure mask used for EUV exposure). The shape may be, for example, a circle, an ellipse, a rectangle, a line, or a combination of one or more of these. A plurality of openings OP may be formed in the resist film RM. Each of the plurality of openings OP may have a hole shape and may form an array pattern arranged at regular intervals. Also, each of the plurality of openings OP may have a line shape and may be arranged at regular intervals to form a line-and-space pattern.

[0152] According to the second method, a developed pattern consisting of the unexposed second region RM2 can be formed by the development process. As a result, a pattern (e.g., a hole array pattern) different from that of the first method can be formed in the resist film RM. The second method also includes a step ST220 of developing with a first selectivity and a step ST222 of developing with a second selectivity different from the first selectivity. This allows the shape of the developed pattern to be adjusted. Even if the intensity of the exposure reaction differs in the thickness direction in the resist film RM, the first region RM1 can be removed with an appropriate selectivity relative to the second region RM2, and deterioration of the pattern shape and roughness can be suppressed.

[0153] Similarly to step ST12, the development process in step ST22 may be performed using a plasma processing apparatus system (see FIGS. 2 and 3) and / or a liquid processing system (see FIG. 4). Similarly to the first method, when the substrate W is dry-developed using a heat processing system or a plasma processing system, the second method may include a desorption step. The desorption step may be performed after step ST22, and may be repeated one or more times between developments in step ST22.

[0154] In one embodiment, the development process in step ST22 may be performed by both a heat treatment and a plasma treatment. For example, step ST220 may be performed by a heat treatment and step ST222 may be performed by a plasma treatment, or step ST220 may be performed by a plasma treatment and step ST222 may be performed by a heat treatment.

[0155] In one embodiment, in step ST22, a cycle including step ST220 and step ST222 may be repeated multiple times. In this case, the cycle of step ST220 and step ST222 may be repeated multiple times by only dry development, or may be repeated multiple times by only wet development. In addition, after performing the cycle of step ST220 and step ST222 by wet development once or more, the cycle of step ST220 and step ST222 may be performed by dry development once or more. In addition, the cycle of step ST220 by wet development and step ST222 by dry development may be repeated multiple times. Note that, as described above, when the cycle of step ST220 and step ST222 is repeated multiple times, the development conditions of step ST220 and / or step ST222 may be different between one or more cycles and one or more other cycles. For example, the temperature of the substrate support in step ST220 may be lower in one or more cycles for developing to a second depth that is deeper than the first depth than in one or more cycles for developing to a first depth.

[0156] In one embodiment, after step ST22, the base film UF is etched. The etching process may be performed, for example, by generating plasma from a processing gas in the processing chamber 10 of the plasma processing device 1. In the etching process, the resist film RM functions as a mask, and a recess is formed in the base film UF based on the shape of the opening OP. When development is performed using the plasma processing device 1 in step ST22, the etching process may be performed consecutively in the same processing chamber 10 as step ST22, or may be performed in a processing chamber 10 of another plasma processing device 1.

[0157] <Example of substrate processing system configuration> 16 is a block diagram for explaining a configuration example of a substrate processing system SS according to an exemplary embodiment. The substrate processing system SS includes a first carrier station CS1, a first processing station PS1, a first interface station IS1, an exposure apparatus EX, a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a controller CT.

[0158] The first carrier station CS1 loads and unloads the first carrier C1 between the first carrier station CS1 and a system external to the substrate processing system SS. The first carrier station CS1 has a mounting table including a plurality of first mounting plates ST1. The first carrier C1 is mounted on each of the first mounting plates ST1 in a state in which it contains a plurality of substrates W or in an empty state. The first carrier C1 has a housing capable of housing a plurality of substrates W therein. The first carrier C1 is, for example, a Front Opening Unified Pod (FOUP).

[0159] The first carrier station CS1 transports the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further includes a first transport device HD1. The first transport device HD1 is provided in the first carrier station CS1 so as to be located between the placement table and the first processing station PS1. The first transport device HD1 transports and delivers the substrate W between the first carrier C1 on each first placement plate ST1 and the second transport device HD2 of the first processing station PS1. The substrate processing system SS may further include a load lock module. The load lock module may be provided between the first carrier station CS1 and the first processing station PS1. The load lock module can switch the internal pressure to atmospheric pressure or vacuum. The "atmospheric pressure" may be the pressure inside the first transport device HD1. The "vacuum" may be a pressure lower than atmospheric pressure, and may be a medium vacuum of, for example, 0.1 Pa to 100 Pa. The inside of the second transport device HD2 may be at atmospheric pressure or vacuum. The load lock module may, for example, transport a substrate W from the first transport device HD1 at atmospheric pressure to the second transport device HD2 at vacuum, and transport a substrate W from the second transport device HD2 at vacuum to the first transport device HD1 at atmospheric pressure.

[0160] The first processing station PS1 performs various processes on the substrate W. In one embodiment, the first processing station PS1 includes a pre-processing module PM1, a resist film forming module PM2, and a first thermal processing module PM3 (hereinafter collectively referred to as the "first substrate processing module PMa"). The first processing station PS1 also has a second transfer device HD2 that transfers the substrate W. The second transfer device HD2 transfers and delivers the substrate W between two designated first substrate processing modules PMa, and between the first processing station PS1 and the first carrier station CS1 or the first interface station IS1.

[0161] In the pre-treatment module PM1, the substrate W is subjected to pre-treatment. In one embodiment, the pre-treatment module PM1 includes a temperature adjustment unit that adjusts the temperature of the substrate W, a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision, and the like. In one embodiment, the pre-treatment module PM1 includes a surface modification treatment unit that performs a surface modification treatment on the substrate W. Each treatment unit of the pre-treatment module PM1 may include a heat treatment device 100 (see FIG. 1), a plasma treatment device 1 (see FIGS. 2 and 3), and / or a liquid treatment device 300 (see FIG. 4).

[0162] In the resist film forming module PM2, a resist film is formed on the substrate W. In one embodiment, the resist film forming module PM2 includes a dry coating unit. The dry coating unit forms a resist film on the substrate W using a dry process such as a vapor phase deposition method. In one example, the dry coating unit includes a CVD apparatus or an ALD apparatus that performs chemical vapor deposition of a resist film on the substrate W arranged in a chamber, or a PVD apparatus that performs physical vapor deposition of a resist film. The dry coating unit may be a thermal processing apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0163] In one embodiment, the resist film forming module PM2 includes a wet coating unit. The wet coating unit forms a resist film on the substrate W using a wet process such as a liquid phase deposition method. The wet coating unit may be, for example, a liquid processing apparatus 300 (see FIG. 4).

[0164] In one embodiment, an example of the resist film formation module PM2 includes both a wet coating unit and a dry coating unit.

[0165] In the first thermal treatment module PM3, the substrate W is subjected to thermal treatment. In one embodiment, the first thermal treatment module PM3 includes one or more of a pre-bake (PAB) unit that performs a heat treatment on the substrate W on which a resist film is formed, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0166] The first interface station IS1 has a third transfer device HD3. The third transfer device HD3 transfers and delivers the substrate W between the first processing station PS1 and the exposure device EX. The third transfer device HD3 has a housing that houses the substrate W, and may be configured so that the temperature, humidity, pressure, etc. within the housing can be controlled.

[0167] The exposure apparatus EX uses an exposure mask (reticle) to expose a resist film on the substrate W. The exposure apparatus EX may be, for example, an EUV exposure apparatus having a light source that generates EUV light.

[0168] The second interface station IS2 has a fourth transfer device HD4. The fourth transfer device HD4 transfers and delivers the substrate W between the exposure apparatus EX and the second processing station PS2. The fourth transfer device HD4 has a housing that houses the substrate W, and may be configured so that the temperature, humidity, pressure, etc. within the housing can be controlled.

[0169] The second processing station PS2 performs various processes on the substrate W. In one embodiment, the second processing station PS2 includes a second thermal treatment module PM4, a measurement module PM5, a developing module PM6, and a third thermal treatment module PM7 (hereinafter collectively referred to as "second substrate processing module PMb"). The second processing station PS2 also has a fifth transfer device HD5 that transfers the substrate W. The fifth transfer device HD5 transfers and delivers the substrate W between two designated second substrate processing modules PMb, and between the second processing station PS2 and the second carrier station CS2 or the second interface station IS2.

[0170] In the second thermal treatment module PM4, the substrate W is subjected to a thermal treatment. In one embodiment, the thermal treatment module PM4 includes one or more of a post-exposure bake (PEB) unit that heat-treats the substrate W after exposure, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0171] In the measurement module PM5, various measurements are performed on the substrate W. In one embodiment, the measurement module PM5 includes an imaging unit including a mounting stage for mounting the substrate W, an imaging device, an illumination device, and various sensors (temperature sensor, reflectance measurement sensor, etc.). The imaging device may be, for example, a CCD camera that captures an image of the appearance of the substrate W. Alternatively, the imaging device may be a hyperspectral camera that captures images by dispersing light into wavelengths. The hyperspectral camera may measure one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film.

[0172] In the developing module PM6, the substrate W is subjected to a developing process. In one embodiment, the developing module PM6 includes a dry developing unit that performs dry development on the substrate W. The dry developing unit may be, for example, a thermal processing apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIG. 2 and FIG. 3). In one embodiment, the developing module PM6 includes a wet developing unit that performs wet development on the substrate W. The wet developing unit may be, for example, a liquid processing apparatus 300 (FIG. 4). In one embodiment, the developing module PM6 includes both a dry developing unit and a wet developing unit.

[0173] In the third thermal treatment module PM7, the substrate W is subjected to a thermal treatment. In one embodiment, the third thermal treatment module PM7 includes one or more of a post bake (PB) unit that heat-treats the substrate W after development, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0174] The second carrier station CS2 transfers the second carrier C2 between the second carrier station CS2 and a system outside the substrate processing system SS. The configuration and function of the second carrier station CS2 may be similar to those of the first carrier station CS1 described above.

[0175] The controller CT controls each component of the substrate processing system SS to perform a given process on the substrate W. The controller CT stores a recipe in which a process procedure, process conditions, transport conditions, etc. are set, and controls each component of the substrate processing system SS to perform a given process on the substrate W in accordance with the recipe. The controller CT may have some or all of the functions of each controller (the controller 200 and controller 2, and controller 400 shown in FIGS. 1 to 4).

[0176] <An example of a substrate processing method> FIG. 17 is a flowchart showing a substrate processing method (hereinafter, also referred to as "method MT") according to an exemplary embodiment. As shown in FIG. 17, the method MT includes a step ST100 of performing a pre-treatment on a substrate, a step ST200 of forming a resist film on the substrate, a step ST300 of performing a heat treatment (pre-bake: PAB) on the substrate on which the resist film has been formed, a step ST400 of performing EUV exposure on the substrate, a step ST500 of performing a heat treatment (post-exposure bake: PEB) on the substrate after the exposure, a step ST600 of measuring the substrate, a step ST700 of developing the resist film on the substrate, a step ST800 of performing a heat treatment (post-bake: PB) on the substrate after the development, and a step ST900 of etching the substrate. The method MT may not include one or more of the above steps. For example, the method MT may not include the step ST600, and the step ST700 may be performed after the step ST500.

[0177] The method MT may be performed using a substrate processing system SS shown in Fig. 16. In the following, an example will be described in which a controller CT of the substrate processing system SS controls each part of the substrate processing system SS to perform the method MT on a substrate W.

[0178] (Step ST100: Pretreatment) First, a first carrier C1 accommodating a plurality of substrates W is loaded into a first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on a first mounting plate ST1. Next, the first transfer device HD1 sequentially takes out each substrate W from the first carrier C1 and transfers it to a second transfer device HD2 of the first processing station PS1. The substrate W is transferred to a pre-processing module PM1 by the second transfer device HD2. The pre-processing module PM1 performs pre-processing on the substrate W. The pre-processing may include, for example, one or more of temperature adjustment of the substrate W, formation of a part or all of an undercoat film on the substrate W, heating treatment of the substrate W, and high-precision temperature adjustment of the substrate W. The pre-processing may include a surface modification treatment of the substrate W.

[0179] (Step ST200: Forming a resist film) Next, the substrate W is transported to the resist film forming module PM2 by the second transport device HD2. A resist film is formed on the substrate W by the resist film forming module PM2. In one embodiment, the resist film is formed by a wet process such as a liquid phase deposition method. For example, a resist film is formed by spin-coating a resist film on the substrate W using a wet coating unit of the resist film forming module PM2. In one embodiment, the resist film is formed on the substrate W by a dry process such as a vapor phase deposition method. For example, a resist film is formed by vapor-depositing a resist film on the substrate W using a dry coating unit of the resist film forming module PM2.

[0180] The resist film may be formed on the substrate W by both a dry process and a wet process. For example, after a first resist film is formed on the substrate W by a dry process, a second resist film may be formed on the first resist film by a wet process. In this case, the film thickness, material and / or composition of the first resist film and the second resist film may be the same or different.

[0181] (Process ST300:PAB) Next, the substrate W is transported to the first thermal treatment module PM3 by the second transport device HD2. The substrate W is subjected to a heat treatment (pre-baking: PAB) by the first thermal treatment module PM3. The pre-baking may be performed in an air atmosphere or an inert atmosphere. The pre-baking may be performed by heating the substrate W to 50° C. or more or 80° C. or more. The heating temperature of the substrate W may be 250° C. or less, 200° C. or less, or 150° C. or less. In one example, the heating temperature of the substrate may be 50° C. or more and 250° C. or less. When a resist film is formed by a dry process in step ST200, in one embodiment, the pre-baking may be performed continuously in the dry coating unit that performed step ST200. In one embodiment, after the pre-baking, a process (Edge Bead Removal: EBR) for removing the resist film at the edge of the substrate W may be performed.

[0182] (Step ST400: EUV exposure) Next, the substrate W is transferred by the second transport device HD2 to the third transport device HD3 of the first interface station IS1. The substrate W is then transported by the third transport device HD3 to the exposure device EX. The substrate W is subjected to EUV exposure via an exposure mask (reticle) in the exposure device EX. As a result, a first region that has been subjected to EUV exposure and a second region that has not been subjected to EUV exposure are formed on the substrate W in accordance with the pattern of the exposure mask (reticle).

[0183] (Process ST500:PEB) Next, the substrate W is transferred from the fourth transfer device HD4 of the second interface station IS2 to the fifth transfer device HD5 of the second processing station PS2. The substrate W is then transferred by the fifth transfer device HD5 to the second thermal treatment module PM4. The substrate W is then subjected to a heat treatment (post-exposure bake: PEB) in the second thermal treatment module PM4. The post-exposure bake may be performed in an air atmosphere. The post-exposure bake may be performed by heating the substrate W to a temperature of 180° C. or higher and 250° C. or lower.

[0184] (Process ST600: Measurement) Next, the substrate W is transported to the measurement module PM5 by the fifth transport device HD5. The measurement module PM5 measures the substrate W. The measurement may be an optical measurement or another type of measurement. In one embodiment, the measurement by the measurement module PM5 includes measuring the appearance and / or dimensions of the substrate W using a CCD camera. In one embodiment, the measurement by the measurement module PM5 includes measuring one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0185] In one embodiment, the control unit CT determines whether or not there is an exposure abnormality in the substrate W based on the measured appearance and dimensions of the substrate W and / or the pattern shape, etc. In one embodiment, if the control unit CT determines that there is an exposure abnormality, the substrate W may be reworked or discarded without performing development in step ST700. Reworking of the substrate W may be performed by removing the resist on the substrate W and returning to step ST200 to form a resist film again. Reworking after development may cause damage to the substrate W, but by performing reworking before development, damage to the substrate W can be avoided or suppressed.

[0186] (Process ST700: Development) Next, the substrate W is transported to the developing module PM6 by the fifth transport device HD5. In the developing module PM6, the resist film of the substrate W is developed. The developing process may be performed by dry development or wet development. The developing process may be performed by a combination of dry development and wet development. The developing process in step ST700 may be performed by a first method (see FIG. 5 and FIG. 11) or a second method (see FIG. 12). After or during the developing process, a desorption process may be performed one or more times. The desorption process includes descumming or smoothing the surface of the resist film by using an inert gas such as helium or a plasma of the inert gas. In addition, in the developing module PM6, after the developing process, a part of the base film may be etched using the developed resist film as a mask.

[0187] (Process ST800:PB) Next, the substrate W is transferred by the fifth transfer device HD5 to the third thermal treatment module PM7, where the substrate W is subjected to a thermal treatment (post-baking). The post-baking may be performed in an air atmosphere, and may be performed in an N 2 Or O 2The post-baking may be performed in a reduced pressure atmosphere including a pressure of 1000 to 25000. The post-baking may be performed by heating the substrate W to 150° C. or more and 250° C. or less. The post-baking may be performed in the second heat-treatment module PM4 instead of the third heat-treatment module PM7. In an embodiment, after the post-baking, the measurement module PM4PM5 may perform optical measurement of the substrate W. Such measurement may be performed in addition to or instead of the measurement in the step ST600. In an embodiment, the control unit CT judges the presence or absence of an abnormality such as a defect, a scratch, or the attachment of a foreign substance in the developed pattern of the substrate W based on the measured appearance, dimensions, and / or pattern shape of the substrate W. In an embodiment, if the control unit CT judges that there is an abnormality, the substrate W may be reworked or discarded without etching in the step ST900. In an embodiment, if the control unit CT judges that there is an abnormality, the opening dimension of the resist film of the substrate W may be adjusted using a dry coating unit (CVD device, ALD device, etc.).

[0188] (Process ST900: Etching) After the step ST800 is performed, the substrate W is transferred to the sixth transfer device HD6 of the second carrier station CS2 by the fifth transfer device HD5, and is transferred to the second carrier C2 of the second placement plate ST2 by the sixth transfer device HD6. The second carrier C2 is then transferred to a plasma processing system (not shown). The plasma processing system may be, for example, the plasma processing system shown in FIG. 2 and FIG. 3. In the plasma processing system, the undercoat film UF of the substrate W is etched using the developed resist film as a mask. This completes the method MT. In the step ST700, when the resist film is developed using a plasma processing device, the etching may be performed subsequently in a plasma processing chamber of the plasma processing device. In addition, when the second processing station PS2 includes a plasma processing module in addition to the developing module PM6, the etching may be performed in the plasma processing module. The above-mentioned desorption process may be performed one or more times before or during the etching.

[0189] The embodiments of the present disclosure further include the following aspects.

[0190] (Appendix 1) A method for processing a substrate, comprising: (a) providing a substrate having an undercoat film and a metal-containing resist film on the undercoat film on a substrate support, the metal-containing resist film including a first region and a second region; (b) developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film; The step (b) comprises: (b1) removing the second region with respect to the first region at a first selectivity; (b2) further removing the second region with respect to the first region at a second selectivity different from the first selectivity; A method for processing a substrate.

[0191] (Appendix 2) 2. The substrate processing method of claim 1, wherein the first region is an exposed region and the second region is an unexposed region.

[0192] (Appendix 3) 3. The substrate processing method according to claim 1, wherein the second selectivity is higher than the first selectivity.

[0193] (Appendix 4) In the step (b), the development is carried out by wet development, The step (b) comprises: (I) the solubility of the metal-containing resist film in the developer used in the step (b2) is lower than the solubility of the metal-containing resist film in the developer used in the step (b1); (II) the concentration of the developer used in the step (b2) is lower than the concentration of the developer used in the step (b1); and (III) the temperature of the developer used in the step (b2) is lower than the temperature of the developer used in the step (b1); 4. The substrate processing method according to claim 1, wherein at least one of the following conditions is satisfied:

[0194] (Appendix 5) In the step (b), the development is carried out by dry development in a chamber; The step (b) comprises: (I) the temperature of the substrate supporting part in the step (b2) is lower than the temperature of the substrate supporting part in the step (b1); (II) the pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1); (III) the acidity of the second developing gas used in the step (b2) is lower than the acidity of the first developing gas used in the step (b1); and (IV) the concentration of the second developing gas used in the step (b2) is lower than the concentration of the first developing gas used in the step (b1); 4. The substrate processing method according to claim 1, wherein at least one of the following conditions is satisfied:

[0195] (Appendix 6) The step (b1) is carried out by dry development using a first processing gas containing a first developing gas; The step (b2) is carried out by dry development using a second processing gas containing a second developing gas; The step (b) comprises: (I) the temperature of the substrate supporting part in the step (b2) is lower than the temperature of the substrate supporting part in the step (b1); (II) the pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1); (III) the acidity of the second developing gas is less than the acidity of the first developing gas; (IV) the concentration of the second developing gas is lower than the concentration of the first developing gas; and (V) the second process gas contains a protective gas for protecting the sidewall of the first region exposed in the steps (b1) and (b2), and the first process gas does not contain the protective gas or contains the protective gas at a partial pressure lower than the partial pressure of the protective gas contained in the second process gas; 4. The substrate processing method according to claim 1, wherein at least one of the following conditions is satisfied:

[0196] (Appendix 7) In the step (b), the development is performed by dry development using plasma generated in a chamber; The step (b) comprises: (I) the power level of the source RF signal for plasma generation supplied to the chamber in the step (b2) is lower than the power level of the source RF signal in the step (b1); and (II) the power or voltage level of the bias signal supplied to the chamber in the step (b2) is lower than the power or voltage level of the bias signal in the step (b1); 4. The substrate processing method according to claim 1, wherein at least one of the following conditions is satisfied:

[0197] (Appendix 8) 8. The substrate processing method according to claim 1, wherein the step (b) further includes a step of modifying the first region between the step (b1) and the step (b2).

[0198] (Appendix 9) 9. The substrate processing method according to claim 8, wherein modifying the first region includes heating or plasma processing the substrate.

[0199] (Appendix 10) 10. The substrate processing method according to claim 8, wherein the step of modifying the first region is performed in a chamber in which the step (b1) is performed.

[0200] (Appendix 11) 10. The substrate processing method according to claim 8, wherein the step of modifying the first region is performed in a chamber different from that in the step (b1).

[0201] (Appendix 12) 4. The substrate processing method according to claim 1, wherein in the step (b1), the developing is performed by wet developing, and in the step (b2), the developing is performed by dry developing.

[0202] (Appendix 13) 13. The substrate processing method according to any one of claims 1 to 12, wherein in the step (b), a cycle including the steps (b1) and (b2) is repeated a plurality of times.

[0203] (Appendix 14) 14. The substrate processing method according to claim 1, wherein the metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0204] (Appendix 15) 15. The substrate processing method of claim 1, wherein the first region is exposed to EUV light.

[0205] (Appendix 16) 16. The substrate processing method of claim 1, wherein the step (b1) is switched to the step (b2) based on a depth or an aspect ratio of an opening formed in the metal-containing resist film by the developing.

[0206] (Appendix 17) the first region includes a first portion and a second portion below the first portion and on the undercoat film; 17. The substrate processing method according to claim 1, wherein the step (b1) is performed until just before the second portion is exposed or until a part of the second portion is exposed.

[0207] (Appendix 18) (c) The substrate processing method according to any one of Appendix 1 to Appendix 17, further comprising, after the step (b), a step of etching the undercoat film using the metal-containing resist film as a mask.

[0208] (Appendix 19) a step of removing residue from the first region or the second region generated in the step (b1) after the step (b1) and before the step (b2); a step of removing residues from the first region or the second region generated in the step (b1) and / or the step (b2) after the step (b2) and before the step (c); 19. The substrate processing method of claim 18, further comprising at least one of the following steps.

[0209] (Appendix 20) 20. The substrate processing method according to claim 18, wherein the step (c) is performed in the same chamber as the chamber used in the step (b).

[0210] (Appendix 21) 20. The substrate processing method according to claim 18, wherein the step (c) is performed in a chamber different from a chamber used in the step (b).

[0211] (Appendix 22) A method for processing a substrate, comprising: (a) providing a substrate having an undercoat film and a metal-containing resist film formed on the undercoat film on a substrate support, the metal-containing resist film having a first region that is exposed and a second region that is not exposed; (b) dry developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film; The step (b) comprises: (b1) controlling a temperature of the substrate support to a first temperature to remove the second region; (b2) controlling a temperature of the substrate support to a second temperature lower than the first temperature to remove the second region; A method for processing a substrate.

[0212] (Appendix 23) 23. The substrate processing method according to claim 22, wherein the step (b) is a step of performing the dry developing using HBr, and the first temperature is 20° C. or more and 60° C. or less, and the second temperature is −20° C. or more and 20° C. or less.

[0213] (Appendix 24) A method for processing a substrate, comprising: (a) providing a substrate having an undercoat film and a metal-containing resist film formed on the undercoat film on a substrate support, the metal-containing resist film having a first region that is exposed and a second region that is not exposed; (b) dry developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film; The step (b) comprises: (b1) removing the second region using a first process gas; (b2) removing the second region using a second process gas that is less acidic than the first process gas; A method for processing a substrate.

[0214] (Appendix 25) the first process gas comprises a halogen-containing inorganic acid; The second process gas includes an organic acid. 25. The substrate processing method of claim 24.

[0215] (Appendix 26) the first process gas includes a halogen-containing inorganic acid and an organic acid at a flow rate lower than that of the halogen-containing inorganic acid; The second process gas includes a halogen-containing inorganic acid and an organic acid having a flow rate higher than that of the halogen-containing inorganic acid. 26. The substrate processing method according to claim 24 or 25.

[0216] (Appendix 27) The halogen-containing inorganic acid is HBr gas, HCl gas, BCl 327. The substrate processing method according to claim 25 or 26, comprising a gas, and at least one selected from the group consisting of an HF gas and an HI gas.

[0217] (Appendix 28) 28. The substrate processing method according to claim 25, wherein the organic acid includes at least one selected from the group consisting of a carboxylic acid, a β-dicarbonyl compound, and an alcohol.

[0218] (Appendix 29) The step (b) comprises: (I) the temperature of the substrate support part in the step (b2) is lower than the temperature of the substrate support part in the step (b1); and (II) the pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1); 29. The substrate processing method according to any one of claims 24 to 28, wherein at least one of the following is satisfied.

[0219] (Appendix 30) 30. The substrate processing method according to any one of claims 24 to 29, wherein in the step (b), the steps (b1) and (b2) are repeated.

[0220] (Appendix 31) 31. The substrate processing method according to any one of Appendix 24 to Appendix 30, wherein in the step (b), a cycle including the step (b1) and the step (b2) is performed one or more times, and then the step (b1) is further performed.

[0221] (Appendix 32) The step (b) includes a step of removing the second region using plasma generated from the first process gas and / or the second process gas after a cycle including the steps (b1) and (b2) is performed one or more times without using plasma. 32. The substrate processing method according to any one of claims 24 to 31.

[0222] (Appendix 33) A substrate processing system having one or more substrate processing apparatuses and a control unit, The control unit, with respect to the one or more substrate processing apparatuses, (a) providing a substrate having an undercoat film and a metal-containing resist film on a substrate support, the metal-containing resist film including a first region and a second region; (b) controlling a development of the metal-containing resist film to selectively remove the second region from the metal-containing resist film; The control of (b) is (b1) controlling removal of the second region with respect to the first region at a first selectivity; (b2) further removing the second region with respect to the first region at a second selectivity different from the first selectivity; Substrate processing system.

[0223] The above embodiments are described for the purpose of explanation and are not intended to limit the scope of the present disclosure. Various modifications can be made to each embodiment without departing from the scope and spirit of the present disclosure. For example, some components in one embodiment can be added to other embodiments. Also, some components in one embodiment can be replaced with corresponding components in other embodiments. [Explanation of symbols]

[0224] 1: plasma processing apparatus, 2: control unit, 10: plasma processing chamber, 1: substrate support unit, 20: gas supply unit, 30: power supply, 100: heat processing apparatus, 102: processing chamber, 120: stage heater, 121: substrate support unit, 141: gas nozzle, 200: control unit, 300: liquid processing apparatus, 311: spin chuck, 321: cup, 331: processing liquid supply nozzle, 351: cleaning liquid supply nozzle, 400: control unit, OP: opening, RM: resist film, RM1: first region, RM2: second region, UF: undercoat film, W: substrate

Claims

1. A method for processing a substrate, comprising: (a) providing a substrate having an undercoat film and a metal-containing resist film on the undercoat film on a substrate support, the metal-containing resist film including a first region and a second region; (b) developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film; The step (b) comprises: (b1) removing the second region with respect to the first region at a first selectivity; (b2) further removing the second region with respect to the first region at a second selectivity different from the first selectivity; A method for processing a substrate.

2. 2. The method of claim 1, wherein the first area is an exposed area and the second area is an unexposed area.

3. The substrate processing method of claim 1 , wherein the second selectivity is higher than the first selectivity.

4. In the step (b), the development is performed by wet development, The step (b) comprises: (I) the solubility of the metal-containing resist film in the developer used in the step (b2) is lower than the solubility of the metal-containing resist film in the developer used in the step (b1); (II) the concentration of the developer used in the step (b2) is lower than the concentration of the developer used in the step (b1); and (III) the temperature of the developer used in the step (b2) is lower than the temperature of the developer used in the step (b1); The substrate processing method according to claim 1 , wherein at least one of the above conditions is satisfied.

5. In the step (b), the development is carried out by dry development in a chamber; The step (b) comprises: (I) the temperature of the substrate support part in the step (b2) is lower than the temperature of the substrate support part in the step (b1); (II) the pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1); (III) the acidity of the second developing gas used in the step (b2) is lower than the acidity of the first developing gas used in the step (b1); and (IV) the concentration of the second developing gas used in the step (b2) is lower than the concentration of the first developing gas used in the step (b1); The substrate processing method according to claim 1 , wherein at least one of the above conditions is satisfied.

6. The step (b1) is carried out by dry development using a first processing gas containing a first developing gas; The step (b2) is carried out by dry development using a second processing gas containing a second developing gas; The step (b) comprises: (I) the temperature of the substrate support part in the step (b2) is lower than the temperature of the substrate support part in the step (b1); (II) the pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1); (III) the acidity of the second developing gas is less than the acidity of the first developing gas; (IV) the concentration of the second developing gas is lower than the concentration of the first developing gas; and (V) the second process gas contains a protective gas for protecting the sidewall of the first region exposed in the steps (b1) and (b2), and the first process gas does not contain the protective gas or contains the protective gas at a partial pressure lower than the partial pressure of the protective gas contained in the second process gas; The substrate processing method according to claim 1 , wherein at least one of the above conditions is satisfied.

7. In the step (b), the development is performed by dry development using plasma generated in a chamber; The step (b) comprises: (I) the power level of the source RF signal for plasma generation supplied to the chamber in the step (b2) is lower than the power level of the source RF signal in the step (b1); and (II) the level of power or voltage of the bias signal supplied to the chamber in the step (b2) is lower than the level of power or voltage of the bias signal in the step (b1); The substrate processing method according to claim 1 , wherein at least one of the above conditions is satisfied.

8. 2. The substrate processing method according to claim 1, wherein the step (b) further comprises the step of modifying the first region between the steps (b1) and (b2).

9. The substrate processing method according to claim 8 , wherein the step of modifying the first region includes the step of heating or plasma processing the substrate.

10. 9. The substrate processing method according to claim 8, wherein the step of modifying the first region is performed in the same chamber as the step (b1).

11. The substrate processing method according to claim 8 , wherein the step of modifying the first region is performed in a chamber different from a chamber in which the step (b1) is performed.

12. 2. The substrate processing method according to claim 1, wherein in the step (b1), the developing is performed by wet developing, and in the step (b2), the developing is performed by dry developing.

13. The substrate processing method according to claim 1 , wherein in the step (b), a cycle including the steps (b1) and (b2) is repeated a plurality of times.

14. 14. The substrate processing method according to claim 1, wherein the metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti.

15. The substrate processing method according to claim 1 , wherein the first region is exposed to EUV light.

16. 14. The substrate processing method according to claim 1, wherein switching from the step (b1) to the step (b2) is performed based on a depth or an aspect ratio of an opening formed in the metal-containing resist film by the development.

17. the first region includes a first portion and a second portion below the first portion and on the undercoat film; The substrate processing method according to claim 1 , wherein the step (b1) is performed until just before the second portion is exposed or until a part of the second portion is exposed.

18. 14. The substrate processing method according to claim 1, further comprising: (c) after the step (b), a step of etching the base film using the metal-containing resist film as a mask.

19. a step of removing residue from the first region or the second region generated in the step (b1) after the step (b1) and before the step (b2); a step of removing residues of the first region or the second region generated in the step (b1) and / or the step (b2) after the step (b2) and before the step (c); The method of claim 18 , further comprising at least one of:

20. 20. The substrate processing method according to claim 18, wherein the step (c) is performed in the same chamber as the chamber used in the step (b).

21. 20. The substrate processing method according to claim 18, wherein the step (c) is performed in a chamber different from a chamber used in the step (b).

22. A method for processing a substrate, comprising: (a) providing a substrate having an undercoat film and a metal-containing resist film formed on the undercoat film on a substrate support, the metal-containing resist film having a first region that is exposed to light and a second region that is not exposed to light; (b) dry developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film; The step (b) comprises: (b1) controlling a temperature of the substrate support to a first temperature to remove the second region; (b2) controlling a temperature of the substrate support to a second temperature lower than the first temperature to remove the second region; A method for processing a substrate.

23. 23. The substrate processing method according to claim 22, wherein the step (b) is a step of performing the dry developing using HBr, the first temperature is 20° C. or more and 60° C. or less, and the second temperature is −20° C. or more and 20° C. or less.

24. A method for processing a substrate, comprising: (a) providing a substrate having an undercoat film and a metal-containing resist film formed on the undercoat film on a substrate support, the metal-containing resist film having a first region that is exposed to light and a second region that is not exposed to light; (b) dry developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film; The step (b) comprises: (b1) removing the second region using a first process gas; (b2) removing the second region using a second process gas that is less acidic than the first process gas; A method for processing a substrate.

25. the first process gas comprises a halogen-containing inorganic acid; The second process gas includes an organic acid. The method of claim 24.

26. the first process gas includes a halogen-containing inorganic acid and an organic acid at a flow rate lower than that of the halogen-containing inorganic acid; The second process gas includes a halogen-containing inorganic acid and an organic acid having a flow rate higher than that of the halogen-containing inorganic acid. The method of claim 24.

27. The halogen-containing inorganic acid is HBr gas, HCl gas, BCl ３ 27. The method of claim 25 or 26, further comprising: a gas, and at least one selected from the group consisting of an HF gas and an HI gas.

28. 27. The substrate processing method according to claim 25, wherein the organic acid includes at least one selected from the group consisting of a carboxylic acid, a β-dicarbonyl compound, and an alcohol.

29. The step (b) comprises: (I) the temperature of the substrate support part in the step (b2) is lower than the temperature of the substrate support part in the step (b1); and (II) the pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1); The substrate processing method according to claim 24 , wherein at least one of the following conditions is satisfied.

30. The substrate processing method according to claim 24 , wherein in the step (b), the step (b1) and the step (b2) are repeated.

31. 25. The substrate processing method according to claim 24, wherein in the step (b), a cycle including the step (b1) and the step (b2) is performed one or more times, and then the step (b1) is further performed.

32. The step (b) includes a step of removing the second region using plasma generated from the first process gas and / or the second process gas after a cycle including the steps (b1) and (b2) is performed one or more times without using plasma. The method of claim 24.

33. A substrate processing system having one or more substrate processing apparatuses and a control unit, the substrate processing apparatus is configured to process a substrate on a substrate support, the substrate having an undercoat film and a metal-containing resist film on the undercoat film, the metal-containing resist film including a first region and a second region; The control unit, with respect to the one or more substrate processing apparatuses, (a) controlling the provision of the substrate on the substrate support; (b) controlling a developing process for selectively removing the second region from the metal-containing resist film; The control of (b) is (b1) controlling removal of the second region with respect to the first region at a first selectivity; (b2) further removing the second region with respect to the first region at a second selectivity different from the first selectivity; Substrate processing system.

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