Substrate processing method and substrate processing system

Abstract

To provide a technique for adjusting the shape of a development pattern.SOLUTION: A substrate processing method includes: a step (a) of providing a substrate having a base film and a metal-containing resist film on the base film, onto a substrate support, the metal-containing resist film including a first region and a second region; and a step (b) of developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film. The step (b) comprises: a step (b1) of removing the second region against a first region at a first selection ratio; and a step (b2) of further removing the second region against the first region at a second selection ratio that is different from the first selection ratio.SELECTED DRAWING: Figure 5

Description

Technical Field

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

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure provides a technique for adjusting the shape of a developed pattern.

Means for Solving the Problems

[0005] In one exemplary embodiment of the present disclosure, a substrate processing method includes: (a) providing a substrate having an underlying film and a metal-containing resist film on the underlying film on a substrate support portion, 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 respect to the first region at a first selection ratio; and (b2) further removing the second region with respect to the first region at a second selection ratio different from the first selection ratio.

Effects of the Invention

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

Brief Description of the Drawings

[0007]

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Embodiments for Carrying Out the Invention

[0008] Hereinafter, each embodiment of the present disclosure will be described.

[0009] In one exemplary embodiment, there is provided a step of providing a substrate having a base film and a metal-containing resist film on the base film on a substrate support portion, wherein the metal-containing resist film includes a first region and a second region, and a step of developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film, and the step of (b) includes a step of removing the second region with respect to the first region at a first selection ratio, and a step of further removing the second region with respect to the first region at a second selection ratio different from the first selection ratio, and a substrate processing method is provided.

[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 selection ratio is higher than the first selection ratio.

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

[0013] In one exemplary embodiment, in step (b), the development is performed by dry development in a chamber, and step (b) satisfies at least one of the following: (I) the temperature of the substrate support in step (b2) is lower than the temperature of the substrate support in step (b1); (II) the pressure in the chamber in step (b2) is lower than the pressure in the chamber in step (b1); (III) the acidity of the second developing gas used in step (b2) is less than the acidity of the first developing gas used in step (b1); and (IV) the concentration of the second developing gas used in step (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 processing gas containing a first developing gas, (b2) is performed by dry development using a second processing gas containing a second developing gas, and step (b) satisfies at least one of the following: (I) the temperature of the substrate support in step (b2) is lower than the temperature of the substrate support in step (b1); (II) the pressure in the chamber in step (b2) is lower than the pressure in the chamber in 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 processing gas contains a protective gas that protects the sidewalls of the first region exposed in steps (b1) and (b2), and the first processing gas either 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 processing gas.

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

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

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

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

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

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

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

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

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

[0024] In one exemplary embodiment, the switching from the step of (b1) to the step of (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 on the underlying film below the first portion, and the step of (b1) is performed until immediately before the second portion is exposed or until a part of the second portion is exposed.

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

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

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

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

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

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

[0032] In one exemplary embodiment, there is provided a substrate processing method including a step (a) of providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion, wherein the metal-containing resist film has an exposed first region and an unexposed second region, and a step (b) of dry-developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film, and the step (b) includes a step (b1) of removing the second region using a first processing gas, and a step (b2) of removing the second region using a second processing gas having a lower acidity than the first processing gas.

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

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

[0035] In one exemplary embodiment, the halogen-containing inorganic acid contains 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 contains at least one selected from the group consisting of carboxylic acid, β-dicarbonyl compound, and alcohol.

[0037] In one exemplary embodiment, in the step (b), at least one of the following is satisfied: (I) the temperature of the substrate support in the step (b2) is lower than the temperature of the substrate support 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).

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

[0039] In one exemplary embodiment, in the step (b), after the cycle including the steps (b1) and (b2) is performed one or more times, the step (b1) is further performed.

[0040] In one exemplary embodiment, the step (b) includes a step of removing the second region using plasma generated from the first processing gas and / or the second processing gas after the cycle including the steps (b1) and (b2) is 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 control unit. The control unit is configured to perform, on the one or more substrate processing apparatuses, (a) control to provide a substrate having an underlayer film and a metal-containing resist film on the underlayer film on a substrate support portion, wherein the metal-containing resist film includes a first region and a second region, and (b) control to develop the metal-containing resist film to selectively remove the second region from the metal-containing resist film. The control in (b) includes (b1) control to remove the second region from the first region at a first selection ratio, and (b2) control to further remove the second region from the first region at a second selection ratio different from the first selection ratio.

[0042] Hereinafter, each embodiment of the present disclosure will be described in detail with reference to the drawings. In the drawings, the same or similar elements are denoted by the same reference numerals, and redundant descriptions are omitted. Unless otherwise specified, the positional relationships such as up, down, left, and right are described based on the positional relationships shown in the drawings. The dimensional ratios in the drawings do not represent actual ratios, and the actual ratios are not limited to the ratios shown in the drawings.

[0043] <Configuration Example of Heat Treatment System> FIG. 1 is a diagram for explaining a configuration example 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 able to form a sealed space. The processing chamber 102 is, for example, an airtight cylindrical container and is configured to be able to adjust 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. The ceiling surface 140 of the ceiling wall (top plate) of the processing chamber 102 is formed as a horizontal flat surface, and its temperature is adjusted by the ceiling heater 130.

[0045] On the lower side within the processing chamber 102, a substrate support portion 121 is provided. The substrate support portion 121 has a substrate support surface on which a substrate W is supported. The substrate support portion 121 is, for example, formed in a circular shape in 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 portion 121. This stage heater 120 can heat the substrate W placed on the substrate support portion 121. Note that a ring assembly (not shown) may be arranged around the substrate W on the substrate support portion 121. The ring assembly may include one or a plurality of annular members. By arranging 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 composed of an inorganic material or an organic material according to the intended heat treatment.

[0046] The substrate support portion 121 is supported within the processing chamber 102 by columns 122 provided on the bottom surface of the processing chamber 102. A plurality of lift pins 123 that can move vertically are provided on the outer side in the circumferential direction of the columns 122. Each of the plurality of lift pins 123 is inserted into a through hole provided in the substrate support portion 121. The plurality of lift pins 123 are arranged at intervals in the circumferential direction. The lifting operation of the plurality of lift pins 123 is controlled by a lifting mechanism 124. When the lift pins 123 project from the surface of the substrate support portion 121, the transfer of the substrate W between a transfer mechanism (not shown) and the substrate support portion 121 becomes possible.

[0047] An exhaust port 131 having an opening is provided in the side wall 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. By adjusting the exhaust flow rate, etc. by this exhaust mechanism 132, the pressure within the processing chamber 102 is adjusted. Note that a transfer port for the substrate W (not shown) is formed in the side wall of the processing chamber 102 at a position different from the position where the exhaust port 131 opens and can be opened and closed freely.

[0048] In addition, a gas nozzle 141 is provided at a position on the side wall of the processing chamber 102 different from the exhaust port 131 and the transfer port of the substrate W. The gas nozzle 141 supplies a processing gas into the processing chamber 102. The gas nozzle 141 is provided on the side wall of the processing chamber 102 on the opposite side of the exhaust port 131 when viewed from the center of the substrate support portion 121. That is, the gas nozzle 141 is provided symmetrically with the exhaust port 131 with respect to the vertical virtual plane passing through the center of the substrate support portion 121 on the side wall of the processing chamber 102.

[0049] The gas nozzle 141 is formed in a rod shape protruding from the side wall of the processing chamber 102 toward the center side of the processing chamber 102. The tip of the gas nozzle 141 extends horizontally, for example, from the side wall of the processing chamber 102. The processing gas is discharged into the processing chamber 102 from the discharge port opening at the tip of the gas nozzle 141, flows in the direction of the arrow of the dashed line shown in FIG. 1, and is exhausted from the exhaust port 131. Note that the tip of the gas nozzle 41 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] Note that the gas nozzle 141 may be provided on the ceiling wall of the processing chamber 102, for example. Also, the exhaust port 131 may be provided on the bottom surface of the processing chamber 102.

[0051] The heat treatment apparatus 100 has a gas supply pipe 152 connected to the gas nozzle 141 from the outside of the processing chamber 102. A pipe 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 controller. The gas supply unit may include a vaporizer for vaporizing a material in a liquid state.

[0052] The control unit 200 processes computer-executable instructions that cause the heat treatment apparatus 100 to execute various processes described in the present disclosure. The control unit 200 can be configured to control each element of the heat treatment apparatus 100 to execute the various processes described herein. In one embodiment, part or all of the control unit 200 may be included in the heat treatment apparatus 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 can be configured to perform various control operations by reading a program from the storage unit 200a2 and executing the read program. 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 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 CPU (Central Processing Unit). The storage unit 200a2 may include a RAM (Random Access Memory), a ROM (Read Only Memory), an HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 may communicate with the heat treatment apparatus 100 via a communication line such as a LAN (Local Area Network).

[0053] <Configuration Example of Plasma System> FIG. 2 is a diagram for explaining a configuration example when a plasma processing system is used as a development processing system. In one embodiment, the plasma processing system includes a plasma processing apparatus 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing apparatus 1 is an example of a substrate processing apparatus. The plasma processing apparatus 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. Further, the plasma processing chamber 10 has at least one gas supply port for supplying at least one processing gas to the plasma processing space and at least one gas discharge port for discharging gas from the plasma processing space. The gas supply port is connected to a gas supply unit 20 described later, and the gas discharge 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 generation 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 capacitively coupled plasma (CCP), inductively coupled plasma (ICP), ECR plasma (Electron-Cyclotron-resonance plasma), helicon wave plasma (HWP), surface wave plasma (SWP), or the like. Also, various types of plasma generation units including an AC (Alternating Current) plasma generation unit and a DC (Direct Current) plasma generation unit may be used. In one embodiment, the AC signal (AC power) used in the AC plasma generation unit has a frequency in the range of 100 kHz to 10 GHz. Therefore, the AC signal includes RF (Radio Frequency) signals and microwave signals. 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 execute various processes described in the present disclosure. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to execute the various processes described herein. In one embodiment, 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 configuration of the control unit 2 may be the same as each configuration of the control unit 200 (see FIG. 1) described above.

[0056] Hereinafter, a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1 will be described. FIG. 3 is a diagram for explaining a configuration example of the capacitively coupled plasma processing apparatus.

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

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

[0059] In one embodiment, the main body portion 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive member. The conductive member of the base 1110 can 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 in 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. Further, at least one RF / DC electrode coupled to an RF power supply 31 and / or a DC power supply 32 described later may be disposed in the ceramic member 1111a. In this case, 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 at least one RF / DC electrode, the RF / DC electrode is also referred to as a bias electrode. Note that the conductive member of the base 1110 and at least one RF / DC electrode may function as a plurality of lower electrodes. Further, the electrostatic electrode 1111b may function as a lower electrode. Accordingly, the substrate support portion 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 ring is formed of a conductive material or an insulating material, and the cover ring is formed of an insulating material.

[0061] Further, the substrate support portion 11 may include a temperature control 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 control module may include a heater, a heat transfer medium, a flow path 1110a, or a combination thereof. A heat transfer fluid such as brine or gas flows through the flow path 1110a. In one embodiment, the flow path 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111. Further, the substrate support portion 11 may include a heat transfer gas supply portion 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 process 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 a plurality of gas introduction ports 13c. The process 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 plurality of gas introduction ports 13c. Further, the shower head 13 includes at least one upper electrode. The gas introduction portion may include, in addition to the shower head 13, one or more side gas injectors (SGI) attached to one or more openings formed in the side wall 10a.

[0063] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one process gas from the corresponding gas source 21 to the shower head 13 via the corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Further, the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of at least one process gas.

[0064] The power supply 30 includes an RF power supply 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The RF power supply 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. Thereby, plasma is formed from at least one process gas supplied to the plasma processing space 10s. Accordingly, the RF power supply 31 can function as at least a part of the plasma generation unit 12. Also, by supplying a bias RF signal to at least one lower electrode, a bias potential is generated on the substrate W, and the ion component in the formed plasma can be drawn into the substrate W.

[0065] In one embodiment, the RF power supply 31 includes a first RF generation unit 31a and a second RF generation unit 31b. The first RF generation 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 generation 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 generation unit 31b is coupled to at least one lower electrode via at least one impedance matching circuit and is 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 generation 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] Further, the power supply 30 may include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generation unit 32a and a second DC generation unit 32b. In one embodiment, the first DC generation unit 32a is connected to at least one lower electrode and is configured to generate a first DC signal. The generated first DC signal is applied to at least one lower electrode. In one embodiment, the second DC generation unit 32b is connected to at least one upper electrode and is configured to generate a second DC signal. The generated second DC signal is applied to 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 pulse waveform that is rectangular, trapezoidal, triangular, or a combination thereof. In one embodiment, a waveform generation unit for generating a sequence of voltage pulses from a DC signal is connected between the first DC generation unit 32a and at least one lower electrode. Accordingly, the first DC generation unit 32a and the waveform generation unit constitute a voltage pulse generation unit. When the second DC generation unit 32b and the waveform generation unit constitute a voltage pulse generation unit, the voltage pulse generation unit 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 within one cycle. Note that the first and second DC generation units 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generation unit 32a may be provided in place of the second RF generation unit 31b.

[0069] The exhaust system 40 can be connected to, for example, a gas outlet 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 turbo molecular pump, a dry pump, or a combination thereof.

[0070] <Configuration Example of Liquid Processing System> FIG. 4 is a diagram for explaining a configuration example 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] As shown in FIG. 4, the liquid processing apparatus 300 has a spin chuck 311 as a substrate support portion inside the processing chamber 310. The spin chuck 311 holds the substrate W horizontally. The spin chuck 311 is connected to a rotatable lifting portion 312, and the rotatable lifting portion 312 is connected to a rotation driving portion 313 constituted by a motor or the like. By driving the rotation driving portion 313, the substrate W held by the spin chuck 311 can rotate.

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

[0073] Above the inside of the processing chamber 310 of the liquid processing apparatus 300, a blower device 314 is provided to supply air with required temperature and humidity into the cup 321 as a downflow.

[0074] When forming a paddle of the processing liquid on the substrate W, a processing liquid supply nozzle 331 is used. The processing liquid supply nozzle 331 is provided on a nozzle support portion 332 such as an arm, for example. The nozzle support portion 332 is movable up and down like a reciprocating arrow A shown by a broken line in the figure and movable horizontally like a reciprocating arrow B shown by a broken line by a driving mechanism. The processing liquid (resist liquid, developing liquid, 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, in the case of using a so-called long nozzle having a discharge port with a length equal to or greater than the diameter of the substrate W, a paddle of the processing liquid can be formed on the substrate W by scanning from one end to the other end on the substrate W. In the case of a so-called straight type nozzle that discharges a liquid column with 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, so that the processing liquid can be diffused over the entire surface of the substrate W to form a paddle of the processing liquid on the substrate W. Further, the formation of the paddle of the processing liquid may be performed by scanning the straight type nozzle on the substrate W in the same manner as the long nozzle, or by arranging discharge ports for discharging the liquid in the same manner as the straight type on a plurality of substrates W and supplying the processing liquid from each discharge port.

[0076] The gas nozzle 341 has a nozzle body 342. The nozzle body 342 is provided on a nozzle support portion such as an arm, and the nozzle support portion is movable up and down like the reciprocating arrow C shown by the broken line in the figure and horizontally movable like the reciprocating arrow D shown by the broken line by a driving mechanism.

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

[0078] The gas nozzle 341 is also provided with a cleaning liquid supply nozzle 351 for cleaning the processing liquid after liquid processing from the substrate W. The cleaning liquid supply nozzle 351 communicates with 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 located between the two nozzle discharge ports 343 and 344 described above, but its position is not limited to this. The cleaning liquid supply nozzle 351 may have a configuration independent of the gas nozzle 341.

[0079] The control unit 400 processes computer-executable instructions for causing the liquid processing apparatus 300 to execute various processes described in the present disclosure. The control unit 400 may be configured to control each element of the liquid processing apparatus 300 so as to execute the various processes described herein. In one embodiment, part or all of the control unit 400 may be included in the liquid processing apparatus 300. The control unit 400 is realized, for example, by a computer 400a. The computer 400a may include a processing unit 400a1, a storage unit 400a2, and a communication interface 400a3. Each configuration of the control unit 400 may be the same as each configuration of the control unit 200 (see FIG. 1) described above.

[0080] <First Embodiment of Substrate Processing Method> FIG. 5 is a flowchart showing an exemplary substrate processing method (hereinafter also referred to as "the first method") according to the first embodiment. 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 developing process in step ST12 is performed by a dry process (hereinafter also referred to as "dry development") using a processing gas. In one embodiment, the developing process in step ST12 is performed by a wet process (hereinafter also referred to as "wet development") using a developing solution. In one embodiment, the developing process in step ST12 is performed using both wet development and dry development.

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

[0082] (Step ST11: Provision of 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 portion 121 via the lifting pins 123. After the substrate W is disposed on the substrate support portion 121, the temperature of the substrate support portion 121 is adjusted to a set temperature. The temperature adjustment of the substrate support portion 121 may be performed by controlling the output of one or more of the side wall heater 104, the stage heater 120, the ceiling heater 130, and the pipe heater 160 (hereinafter also collectively referred to as "each heater"). In this processing method, the temperature of the substrate support portion 121 may be adjusted to the set temperature before step ST11. That is, after the temperature of the substrate support portion 121 is adjusted to the set temperature, the substrate W may be provided on the substrate support portion 121.

[0083] FIG. 6 is a diagram showing an example of the cross-sectional structure of the substrate W provided in step ST11. The substrate W includes an underlayer film UF and a resist film RM formed on the underlayer film UF. The substrate W may be used for the manufacture of 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 containing a metal. The metal may include, for example, 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 contain an organic substance.

[0085] As shown in FIG. 6, the resist film RM has an exposed first region RM1 and an unexposed second region RM2. The first region RM1 is a region exposed to EUV light, i.e., an EUV exposure region. The second region RM2 is a region 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 underlying film UF may be an organic film, a dielectric film, a metal film, or a semiconductor film formed on the silicon wafer, or a laminated film thereof. In one embodiment, the underlying film UF includes, for example, at least one selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film.

[0087] FIGS. 7 and 8 are diagrams showing an example of the underlying film UF of the substrate W, respectively. As shown in FIG. 7, the underlying 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 underlying film UF may be composed of the second film UF2 and the third film UF3.

[0088] The first film UF1 is, for example, a spin-on glass (SOG) film, a SiC film, a SiON film, a silicon-containing antireflection 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 laminated silicon-containing films. For example, the third film UF3 may be composed of an alternately laminated silicon oxide film and a silicon nitride film. Also, the third film UF3 may be composed of an alternately laminated silicon oxide film and a polycrystalline silicon film. Further, the third film UF3 may be a laminated film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. Also, the third film UF3 may be composed of an alternately laminated silicon oxide film and a silicon carbonitride film. Further, 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 underlayer film that has been subjected to an adhesion treatment or the like. The film formation may be performed by a dry process, may be performed by a wet process such as a solution coating method, or may be performed by both a dry process and a wet process. Note that, before the formation of the photoresist film, a surface modification treatment of the underlayer film may be performed. The substrate after the formation of the photoresist film is subjected to a heat treatment, that is, post apply bake (PAB). An additional heat treatment may be performed on the substrate after PAB. The wafer after the heat treatment is transported to an exposure apparatus, and the photoresist film is irradiated with EUV light through an exposure mask (reticle). As a result, a substrate W including an underlayer film UF and a resist film RM having an exposed first region RM1 and an unexposed second region RM2 is formed. 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 substrate after exposure is transported from the exposure apparatus to a heat treatment apparatus under atmosphere control and is subjected to a heat treatment, that is, post exposure bake (PEB). An additional heat treatment may be performed on the substrate W after PEB.

[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 FIGS. 6 to 8, hereinafter also referred to as the "depth direction"). This is considered to be due to the probabilistic fluctuation of the photon distribution of EUV and the shallowness of the depth of focus. In the examples shown in FIGS. 6 to 8, the first region RM1 has, along the thickness direction, a first portion RM1a and a second portion RM1b where the exposure reaction is weaker than the first portion RM1a. The second portion RM1b is a portion in the first region RM1 that is in contact with the underlayer UF.

[0091] In the second part RM1b, since the exposure reaction is weak, it is similar in film properties to the second region RM2 which is the unexposed area. Therefore, in the resist film RM shown in FIGS. 6 to 8, it is difficult to obtain a development contrast (the ratio of the development rates of the exposed area and the unexposed area) along the thickness direction. When the resist film RM is developed under the same conditions along the thickness direction, as the development progresses, the side surface of the lower part (the second part RM1b) of the first region RM1 is likely to be removed together with the second region RM2.

[0092] FIG. 9 is a diagram showing an example of the cross-sectional structure of the substrate W after development. FIG. 9 is an example when the substrate W shown in FIG. 6 is developed under the same conditions along the thickness direction. In the example shown in FIG. 9, in the first region RM after development, the cross-sectional dimension of the second part RM1b becomes smaller along the thickness direction, and it has an inverse taper shape. It is considered that this is because the second part 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 part RM1a, and is likely to be removed by development together with the second region RM2. For this reason, in the first method, the process ST121 and the process ST122 are developed under different conditions. For example, in the first method, the process ST121 and the process ST122 are developed with different development contrasts. Thereby, even when the intensity of the exposure reaction in the resist film RM varies in the thickness direction, the shape of the developed pattern can be adjusted, and deterioration of the pattern shape and roughness can be suppressed.

[0093] (Process ST12: Development of the substrate) Next, in the process ST12, the resist film RM on the substrate W is developed, and the second region RM2 is selectively removed. The process ST12 includes a process ST120 of developing the substrate at a first selection ratio and a process ST122 of developing the substrate at a second selection ratio different from the first selection ratio.

[0094] (Process ST120: Development at the first selection ratio) First, in step ST120, a first processing gas containing a first developing gas is supplied into the processing chamber 102 through the gas nozzle 141. In one embodiment, the first developing gas includes 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 hydrogen halide and / or boron halide. The gas containing a halogen-containing inorganic acid is, for example, at least one selected from the group consisting of HBr gas, BCl3 gas, HCl gas, HF gas, and HI gas. In one embodiment, the first developing gas may be 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 carboxylic acid, β-dicarbonyl compound, and alcohol. In one embodiment, the first developing gas is a gas containing a carboxylic acid. The carboxylic acid is, for example, formic acid (HCOOH), acetic acid (CH3COOH), trichloroacetic acid (CCl3COOH), monofluoroacetic acid (CFH2COOH), difluoroacetic acid (CF2FCOOH), trifluoroacetic acid (CF3COOH), chloro-difluoroacetic acid (CClF2COOH), sulfur-containing acetic acid, thioacetic acid (CH3COSH), thioglycolic acid (HSCH2COOH), trifluoroacetic anhydride ((CF3CO)2O), acetic anhydride ((CH3CO)2O). In one embodiment, the first developing gas includes a β-dicarbonyl compound. The β-dicarbonyl compound is, for example, acetylacetone (CH3C(O)CH2C(O)CH3), trichloroacetylacetone (CCl3C(O)CH2C(O)CH3), hexachloroacetylacetone (CCl3C(O)CH2C(O)CCl3), trifluoroacetylacetone (CF3C(O)CH2C(O)CH3), hexafluoroacetylacetone (HFAc, CF3C(O)CH2C(O)CF3). In one embodiment, the first developing gas includes an alcohol. The alcohol is, for example, nonafluoro-tert-butyl alcohol ((CF3)3C-OH).

[0095] In one embodiment, the first developing gas is a gas containing trifluoroacetic acid. In one embodiment, the first developing gas contains vapor of a halogenated organic acid. The first developing gas, in one example, contains at least one selected from the group consisting of trifluoroacetic anhydride, acetic anhydride, trichloroacetic acid, CFH2COOH, CF2HCOOH, chlorodifluoroacetic acid, sulfur-containing acetic acid, thioacetic acid, and thioglycolic acid. In one embodiment, the first developing gas is a mixed gas of a carboxylic acid and a 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 at a first selection ratio with respect to the first region RM1. In the first method, the "selection ratio" 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 selection ratio may be appropriately set within a range in which the second region RM2 is selectively removed with respect to the first region RM1 (i.e., a value greater than 1). The first selection ratio may be set relatively low such that a part of the first region RM1 is removed. In this case, even if there is a portion that has been EUV-exposed outside the first region RM1 (the portion corresponding to the opening of the exposure mask), the resist film at that portion can be removed and the portion can be prevented from remaining as a residue.

[0097] Step ST120 may be executed until the second region RM2 is removed to a given depth or until the opening formed by development reaches a given aspect ratio. The given depth or aspect ratio may be set based on the progress of the exposure reaction in the first region RM1 (in one example, based on the thicknesses of the first part RM1a and the second part RM1b). In one embodiment, step ST120 may be executed until immediately before or until a part of the second part RM1b of the first region RM1 is exposed.

[0098] FIG. 10 is a diagram showing an example of the cross-sectional structure of the substrate W after the process of 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 at the second selection ratio) In step ST122, a second processing gas containing a second developing gas is supplied into the processing 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 at a second selection ratio different from the first selection ratio with respect to the first region. Making the selection ratio different from the first selection ratio may be performed, for example, by changing any 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, the type and concentration (partial pressure) of the processing gas, etc. from step ST120.

[0101] In one embodiment, the second selection ratio is higher than the first selection ratio. For example, in step ST122, the second selection ratio may be made higher than the first selection ratio 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 121 is made lower than that in step ST120. For example, when using HBr gas as the second developing gas, the set temperature of the substrate support 121 in step ST120 may be 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 121 in step ST122 may be -20°C or higher and less than 20°C. For example, when using BCl3 gas as the second developing gas, the set temperature of the substrate support 121 in step ST120 may be 120°C or higher and 180°C or lower, and the set temperature of the substrate support 121 in step ST122 may be 60°C or higher and less than 120°C.

[0103] (II) In step ST122, the pressure in the processing chamber 102 is made lower than that in step ST120. For example, when using HBr gas as the second developing gas, the pressure in 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 smaller 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 may be changed from HBr gas or BCl3 gas (step ST120) to a carboxylic acid gas such as acetic acid gas (step ST122). Also, for example, 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 BCl3 gas (step ST122). Also, for example, when using a mixed gas as the developing gas, the flow rate (partial pressure) of the "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 each a mixed gas of HBr gas and a carboxylic acid gas, 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 made lower than the concentration (partial pressure) of the developing gas in the processing gas in step ST120. For example, when using a mixed gas containing a developing gas and a noble gas such as Ar as the processing gas, the concentration (partial pressure) of the developing gas in step ST122 is made lower than the concentration (partial pressure) of the developing gas in step 120.

[0106] Step ST122 may be executed until the second region RM2 of the resist film RM is removed and the underlying film UF is exposed. Step ST122 may be performed until a part of the underlying film UF is removed (over-etched) in the depth direction.

[0107] FIG. 11 is a diagram showing an example of the 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 and an opening OP is formed. The opening OP is defined by the side surface of the first region RM1. The opening OP is a space on the underlying film UF surrounded by the side surface. The opening OP has a shape corresponding to the second region RM2 (resulting in a shape corresponding to the exposure mask pattern used for EUV exposure) in a plan view of the substrate W. 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 linear shape and may be arranged at regular intervals to form a line-and-space pattern. Also, a plurality of openings OP may be arranged in a grid pattern to form a pillar pattern.

[0108] As described above, the first method includes step ST120 of developing with a first selection ratio and step ST122 of developing with a second selection ratio different from the first selection ratio. Thereby, the shape of the developed pattern can be adjusted. Also, even when the intensity of the exposure reaction is different in the thickness direction in the resist film RM, the second region RM2 can be removed with an appropriate selection ratio with respect 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 modification of the first method. As shown in FIG. 12, step ST12 may include a 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 heat-treating the substrate W. The heat treatment 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 a temperature of, for example, 190° C. or higher and 240° C. or lower. The substrate W may be heated to a temperature of, for example, 190° C. or higher and 220° C. or lower. The chamber for heating the substrate W may be an atmosphere containing air, N2 gas, and / or H2O gas. By the modification process, the metal film density in the first region RM1 can be increased and the development resistance can be improved. Since a part of the second region RM2 is removed in step ST121 (see FIG. 10), the modification easily proceeds also for the portion RM1b in the first region RM1 where the exposure reaction is weak. Thereby, it is possible to suppress a decrease in development contrast along the depth direction of the resist film RM.

[0111] Note that the heat treatment in step ST121 may be performed in the processing chamber 102 of another heat treatment apparatus 100 different from step ST120 or step ST122. Also, 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 reforming process in step ST121 is performed by plasma treatment. The plasma treatment may be performed, for example, by transporting the substrate W from the heat treatment apparatus 100 to the plasma treatment apparatus 1 and exposing the substrate W to the plasma generated in the plasma treatment apparatus 1. The plasma treatment may be performed, for example, by introducing a processing gas excited by a remote plasma source into the processing chamber 102 of the heat treatment apparatus 100. The processing gas for plasma generation may be an inert gas. The inert gas is, for example, a noble gas such as He, Ar, Ne, Kr, Xe or nitrogen gas.

[0113] In one embodiment, the first method may be executed using a plasma processing system (see FIGS. 2 and 3). For example, the substrate W may be provided on the substrate support portion 11 in the processing chamber 10 of the plasma processing apparatus 1 (step ST11), and dry development of the resist film RM may be performed by supplying a processing gas from the gas supply unit 20 into the processing chamber 10 (step ST12). The processing gas may be the same as in the case of using the heat treatment system. In step ST120 and / or step ST122, a source RF signal may be supplied to the lower electrode of the substrate support portion 11 and / or the upper electrode of the shower head 13. Also, a bias signal may be supplied to the lower electrode of the substrate support portion 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, and development can be promoted.

[0114] When using the plasma processing system, in step ST122, development may be performed at a second selection ratio different from the first selection ratio by changing any 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 portion 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, the power level or voltage level of the bias signal.

[0115] When using the plasma processing system, in step ST122, for example, the second selection ratio may be made higher than the first selection ratio by executing 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 portion 11 is made lower than that in step ST120. For example, when using HBr gas as the processing gas, the set temperature of the substrate support portion 11 in step ST120 may be 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 portion 11 in step ST122 may be -20°C or higher and less than 20°C. For example, when using BCl3 gas as the processing gas, the set temperature of the substrate support portion 11 in step ST120 may be 120°C or higher and 180°C or lower, and the set temperature of the substrate support portion 121 in step ST122 may be 60°C or higher and less than 120°C. Note that the substrate support portion 11 may be adjusted to the set temperature by a temperature control module. Also, the substrate support portion 11 may be adjusted to the set temperature by controlling the pressure of the heat transfer gas (e.g., He) between the electrostatic chuck 1111 and the back surface of the substrate W.

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

[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 may be changed from HBr gas or BCl3 (step ST120) to a carboxylic acid gas such as acetic acid gas (step ST122). Also, for example, 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 may be changed 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 BCl3 gas (step ST122). Also, for example, when a mixed gas is used as the developing gas, the flow rate (partial pressure) of the "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 ST122 are each a mixed gas of HBr gas and a carboxylic acid gas, 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 made lower than the concentration (partial pressure) of the developing gas in the processing gas in step ST120. For example, when a mixed gas containing a 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 made lower than the concentration (partial pressure) of the developing gas in step 120.

[0120] When generating plasma from the processing gas in process ST120 and process ST122, at least one of the following (V) and (VI) may be executed in addition to or instead of the above (I) to (IV). Thereby, the second selection ratio may be made higher than the first selection ratio.

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

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

[0123] In addition, when dry-developing the substrate W using a heat treatment system or a plasma processing system, the first method may include a desorption process. The desorption process includes removing scum (descum) from the surface of the resist film RM or smoothing the surface of the resist film RM with an inert gas such as helium or a plasma of the inert gas. The desorption process may be executed after process ST12. The desorption process may be repeated one or more times between process ST120 and process ST122. Also, the desorption process may be executed instead of between process ST120 and process ST122, or together with between process ST120 and process ST122, before the process of etching the underlying film UF described later and process ST12 (process ST122).

[0124] In one embodiment, the first method may be executed 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 wet development of a resist film RM may be performed by supplying a developing solution from a processing liquid supply nozzle 331 to the substrate W (step ST12). The developing solution may contain, for example, aromatic compounds such as benzene, xylene, and toluene, esters such as propylene glycol monomethyl ester acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone, alcohols such as 4-methyl-2-pentanol, 1-butanol, isopropanol, 1-propanol, and methanol, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and 2-octanone, and ethers such as tetrahydrofuran, dioxane, and anisole.

[0125] When using a liquid processing system, in step ST122, for example, development may be performed at a second selection ratio different from the first selection ratio by changing any one or more of the solubility, concentration, and temperature of the developing solution from step ST120.

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

[0127] (I) Make the solubility of the resist film RM with respect to the developing solution used in step ST122 lower than the solubility of the resist film with respect to the developing solution used in step ST120.

[0128] (II) Make the concentration of the developing solution used in step ST122 lower than the concentration of the developing solution used in step ST120, for example, by increasing the dilution ratio of the developing solution.

[0129] (III) Lower the temperature of the developer used in process ST122 below the temperature of the developer used in process ST120. For example, in process ST120, control the temperature of the developer to be 30°C or higher and 90°C or lower, and in process ST122, control the temperature of the developer to be 10°C or higher and 60°C or lower.

[0130] In one embodiment, the development process in process ST12 may be performed by both dry development and wet development. For example, process ST120 may be executed by wet development using a liquid processing system (see FIG. 4), and process ST122 may be executed by dry development using a heat treatment system (see FIG. 1) or a plasma processing system (see FIGS. 2 and 3). When wet development is performed before dry development, it is possible to suppress contamination due to penetration of the developer into the underlying film UF and pattern collapse of the resist film due to the surface tension of the developer. Note that process ST120 may be executed by dry development, and process ST122 may be executed by wet development.

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

[0132] In one embodiment, in step ST12, a cycle including step ST120 and step ST122 may be repeated a plurality of times. In this case, the cycle of step ST120 and step ST122 may be repeated a plurality of times using only dry development, or may be repeated a plurality of times using only wet development. Also, after performing the cycle of step ST120 and step ST122 one or more times using wet development, the cycle of step ST120 and step ST122 may be performed one or more times using dry development. Further, the cycle of step ST120 performed by wet development and step ST122 performed by dry development may be repeated a plurality of times. As described above, when repeating the cycle of step ST120 and step ST122 a plurality of times, the development conditions of step ST120 and / or step ST122 may be made different between one or more cycles and another one or more cycles. For example, the temperature of the substrate support portion in step ST120 may be made lower in one or more cycles of developing to a second depth deeper than the first depth than in one or more cycles of developing to a first depth.

[0133] In one embodiment, after step ST12, the underlying film UF is subjected to an etching process. The etching process may be performed, for example, by generating plasma from a processing gas in the processing chamber 10 of the plasma processing apparatus 1. In the etching process, the resist film RM functions as a mask, and recesses are formed in the underlying film UF based on the shape of the opening OP. Note that when development is performed using the plasma processing apparatus 1 in step ST12, the etching process may be continuously executed in the same processing chamber 10 as in step ST12, or may be executed in the processing chamber 10 of another plasma processing apparatus 1.

[0134] <Second Embodiment of Substrate Processing Method> FIG. 13 is a flowchart showing an exemplary substrate processing method (hereinafter also referred to as the "second method") according to the second embodiment. 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 executed by the heat treatment system (FIG. 1) described above. Hereinafter, a case where the control unit 200 controls each part of the heat treatment apparatus 100 to execute the second method on the substrate W will be described as an example. The second method may be executed in combination with the heat treatment system (FIG. 1) and other substrate processing systems such as a plasma processing system (FIGS. 2 and 3) and a liquid processing system (FIG. 4).

[0137] (Step ST21: Provision of Substrate) First, in step ST21, the substrate W is provided in the processing chamber 102 of the heat treatment apparatus 100. Step ST21 is the same as step ST11 of the first method, and the configuration of the substrate W may be the same as the configuration shown in FIG. 6.

[0138] (Step ST22: Development of Substrate) Next, in step ST22, the resist film RM on the substrate W is developed, and the first region RM1 is selectively removed. Step ST22 includes a step ST220 of developing the substrate at a first selection ratio and a step ST222 of developing the substrate at a second selection ratio different from the first selection ratio.

[0139] (Step ST220: Development at the First Selection Ratio) First, in step ST220, a processing gas containing a developing gas is supplied into the processing chamber 102 through the gas nozzle 141. Different from step ST120 of the first method described above, the developing gas may be a gas capable of selectively removing the first region with respect to the second region. Thereby, the first region RM1 of the resist film RM is selectively removed with respect to the second region RM2.

[0140] In step ST220, the first region RM1 of the resist film RM is removed with a first selection ratio with respect to the second region RM2. In the second method, the "selection ratio" is also called the 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 selection ratio may be appropriately set within the range in which the first region RM1 is selectively removed with respect 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 the opening formed by development reaches 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 (in one example, based on the thicknesses of the first part RM1a and the second part RM1b). In one embodiment, step ST220 may be performed until immediately before or until a part of the second part RM1b of the first region RM1 is removed.

[0142] FIG. 14 is a diagram showing an example of the cross-sectional structure of the substrate W after the process of 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 part RM1b of the first region is exposed.

[0143] (Step ST222: Development with a second selection ratio) In step ST222, a processing gas containing a developing gas is supplied into the processing 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. Thereby, the first region RM1 of the resist film RM is selectively etched with respect to the second region RM2.

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

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

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

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

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

[0149] (IV) In step ST222, increase the concentration (partial pressure) of the developing gas in the processing gas to be 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 underlying film UF is exposed. Step ST222 may be performed until a part of the underlying film UF is removed (over-etched) in the depth direction.

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

[0152] According to the second method, a development pattern composed of the unexposed second region RM2 can be formed by the development process. Thereby, a pattern different from the first method (for example, a hole array pattern) can be formed in the resist film RM. The second method also includes a step ST220 of developing at a first selection ratio and a step ST222 of developing at a second selection ratio different from the first selection ratio. Thereby, the shape of the development pattern can be adjusted. Also, even when the intensity of the exposure reaction is different in the thickness direction in the resist film RM, the first region RM1 can be removed from the second region RM2 at an appropriate selection ratio, and deterioration of the pattern shape and roughness can be suppressed.

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

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

[0155] In one embodiment, in step ST22, a cycle including steps ST220 and ST222 may be repeated a plurality of times. In this case, the cycle of steps ST220 and ST222 may be repeated a plurality of times only by dry development, or may be repeated a plurality of times only by wet development. Also, after performing the cycle of steps ST220 and ST222 one or more times by wet development, the cycle of steps ST220 and ST222 may be performed one or more times by dry development. Further, the cycle of step ST220 performed by wet development and step ST222 performed by dry development may be repeated a plurality of times. As described above, when the cycle of steps ST220 and ST222 is repeated a plurality of times, the development conditions of step ST220 and / or step ST222 may be made different between one or more cycles and another one or more cycles. For example, the temperature of the substrate support portion in step ST220 may be made lower in one or more cycles of developing to a second depth deeper than the first depth than in one or more cycles of developing to the first depth.

[0156] In one embodiment, after step ST22, the underlying 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 apparatus 1. In the etching process, the resist film RM functions as a mask, and recesses are formed in the underlying film UF based on the shape of the opening OP. When development is performed using the plasma processing apparatus 1 in step ST22, the etching process may be continuously executed in the same processing chamber 10 as in step ST22, or may be executed in the processing chamber 10 of another plasma processing apparatus 1.

[0157] <Configuration Example of Substrate Processing System> FIG. 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 control unit CT.

[0158] The first carrier station CS1 carries in and out a 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. On each first mounting plate ST1, a first carrier C1 in a state of accommodating a plurality of substrates W or in an empty state is mounted. The first carrier C1 has a housing capable of accommodating a plurality of substrates W therein. The first carrier C1 is, for example, a FOUP (Front Opening Unified Pod).

[0159] Also, the first carrier station CS1 conveys the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further includes a first transfer device HD1. The first transfer device HD1 is provided in the first carrier station CS1 so as to be positioned between the mounting table and the first processing station PS1. The first transfer device HD1 transfers and delivers the substrate W between the first carrier C1 on each first mounting plate ST1 and the second transfer 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 pressure inside thereof between atmospheric pressure and vacuum. "Atmospheric pressure" may be the pressure inside the first transfer device HD1. "Vacuum" is a pressure lower than atmospheric pressure and may be, for example, a medium vacuum of 0.1 Pa to 100 Pa. The inside of the second transfer device HD2 may be atmospheric pressure or vacuum. The load lock module may transfer the substrate W, for example, from the first transfer device HD1 at atmospheric pressure to the second transfer device HD2 at vacuum, and also transfer the substrate W from the second transfer device HD2 at vacuum to the first transfer 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 preprocessing module PM1, a resist film forming module PM2, and a first heat treatment module PM3 (hereinafter also collectively referred to as "the first substrate processing module PMa"). The first processing station PS1 also has a second transfer device HD2 for conveying 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 pretreatment module PM1, the substrate W is subjected to pretreatment. In one embodiment, the pretreatment module PM1 includes a temperature adjustment unit for adjusting the temperature of the substrate W, a high-precision temperature control unit for precisely adjusting the temperature of the substrate W, and the like. In one embodiment, the pretreatment module PM1 includes a surface modification processing unit for performing a surface modification process on the substrate W. Each processing unit of the pretreatment module PM1 may be configured to include a heat treatment apparatus 100 (see FIG. 1), a plasma processing apparatus 1 (see FIGS. 2 and 3), and / or a liquid processing apparatus 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 deposition method. The dry coating unit, for example, includes a CVD apparatus or an ALD apparatus for chemically vapor-depositing a resist film or a PVD apparatus for physically vapor-depositing a resist film on the substrate W disposed in the chamber. The dry coating unit may be a heat treatment 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 forming module PM2 includes both a wet coating unit and a dry coating unit.

[0165] In the first heat treatment module PM3, a substrate W is heat-treated. In one embodiment, the first heat treatment module PM3 includes any one or more of a pre-bake (PAB) unit that performs 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 control unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment apparatuses. In one example, the plurality of heat treatment apparatuses may be stacked. The heat treatment apparatus may be, for example, the heat treatment apparatus 100 (see FIG. 1). Each heat 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 apparatus EX. The third transfer device HD3 has a housing that houses the substrate W, and the temperature, humidity, pressure, etc. inside the housing may be configured to be controllable.

[0167] The exposure apparatus EX exposes the resist film on the substrate W using an exposure mask (reticle). 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 the temperature, humidity, pressure, etc. inside the housing may be configured to be controllable.

[0169] The second processing station PS2 performs various processes on the substrate W. In one embodiment, the second processing station PS2 includes a second heat treatment module PM4, a measurement module PM5, a development module PM6, and a third heat treatment module PM7 (hereinafter also collectively referred to as the "second substrate processing module PMb"). Further, the second processing station PS2 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 heat treatment module PM4, heat treatment is performed on the substrate W. In one embodiment, the heat treatment module PM4 includes any one or more of a post-exposure bake (PEB) unit that performs heat treatment on the substrate W after exposure, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature control unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment apparatuses. In one example, a plurality of heat treatment apparatuses may be stacked. The heat treatment apparatus may be, for example, the heat treatment apparatus 100 (see FIG. 1). Each heat 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 that includes a mounting table on which the substrate W is mounted, an imaging device, an illumination device, and various sensors (such as a temperature sensor and a reflectance measurement sensor). The imaging device may be, for example, a CCD camera that images the appearance of the substrate W. Alternatively, the imaging device may be a hyperspectral camera that spectrally divides light for each wavelength and takes a photograph. The hyperspectral camera can measure any 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, method MT includes a step ST100 of performing a pretreatment 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 is 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 exposed substrate, 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 developed substrate, and a step ST900 of etching the substrate. Method MT may not include one or more of the above steps. For example, method MT may not include step ST600, and step ST700 may be executed after step ST500.

[0177] Method MT may be executed using the substrate processing system SS shown in FIG. 16. Hereinafter, a case will be described as an example in which the control unit CT of the substrate processing system SS controls each part of the substrate processing system SS to execute method MT on the substrate W.

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

[0179] (Process ST200: Resist Film Formation) Next, the substrate W is transported to the resist film formation module PM2 by the second transport device HD2. A resist film is formed on the substrate W by the resist film formation module PM2. In one embodiment, the formation of the resist film is performed 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 the wet coating unit of the resist film formation module PM2. In one embodiment, the formation of the resist film on the substrate W is performed by a dry process such as a vapor deposition method. For example, a resist film is formed by depositing a resist film on the substrate W using the dry coating unit of the resist film formation module PM2.

[0180] Note that the formation of the resist film on the substrate W may be performed using both a dry process and a wet process. For example, after forming a first resist film 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 heat treatment module PM3 by the second transfer device HD2. The first heat treatment module PM3 performs a heat treatment (pre-bake: PAB) on the substrate W. The pre-bake may be performed in an air atmosphere or in an inert atmosphere. Also, the pre-bake may be performed by heating the substrate W to 50°C or higher or 80°C or higher. The heating temperature of the substrate W may be 250°C or lower, 200°C or lower, or 150°C or lower. In one example, the heating temperature of the substrate may be 50°C or higher and 250°C or lower. When forming a resist film in a dry process in step ST200, in one embodiment, the pre-bake may be continuously performed in the dry coating unit that executed step ST200. In one embodiment, after the pre-bake, a process of removing the resist film at the edge of the substrate W (Edge Bead Removal: EBR) may be performed.

[0182] (Step ST400: EUV Exposure) Next, the substrate W is delivered by the second transfer device HD2 to the third transfer device HD3 of the first interface station IS1. Then the substrate W is transported to the exposure apparatus EX by the third transfer device HD3. The substrate W undergoes EUV exposure through an exposure mask (reticle) in the exposure apparatus EX. As a result, on the substrate W, a first region where EUV exposure has been performed and a second region where EUV exposure has not been performed are formed corresponding to the pattern of the exposure mask (reticle).

[0183] (Step ST500: PEB) Next, the substrate W is delivered from the fourth transfer device HD4 of the second interface station IS2 to the fifth transfer device HD5 of the second processing station PS2. Then the substrate W is transported to the second heat treatment module PM4 by the fifth transfer device HD5. And a heat treatment (post-exposure bake: PEB) is performed on the substrate W in the second heat treatment module PM4. The post-exposure bake may be performed in an air atmosphere. Also, the post-exposure bake may be performed by heating the substrate W to 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 substrate W is measured by the measurement module PM5. The measurement may be an optical measurement or other measurement. In one embodiment, the measurement by the measurement module PM5 includes measurement of the appearance and / or dimensions of the substrate W using a CCD camera. In one embodiment, the measurement by the measurement module PM5 includes measurement of any 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 the presence or absence of exposure abnormality of the substrate W based on the measured appearance, dimensions, and / or pattern shape, etc. of the substrate W. In one embodiment, when it is determined that there is an exposure abnormality in the control unit CT, rework or discard of the substrate W may be performed without performing development in the process ST700. Rework of the substrate W may be performed by removing the resist on the substrate W and returning to the process ST200 to form a resist film again. Rework after development may involve damage to the substrate W, but by performing rework before development, damage to the substrate W can be avoided or suppressed.

[0186] (Process ST700: Development) Next, the substrate W is transported to the development module PM6 by the fifth transport device HD5. In the development module PM6, the resist film on the substrate W is developed. The development process may be performed by dry development or wet development. The development process may also be performed by combining dry development and wet development. The development process in step ST700 may be performed by the first method (see FIGS. 5 and 11) or the second method (see FIG. 12). One or more desorption processes may be performed after or during the development process. The desorption process includes removing scum (descum) or smoothing the surface from the surface of the resist film with an inert gas such as helium or plasma of the inert gas. Also, in the development module PM6, after the development process, a part of the underlying film may be etched using the developed resist film as a mask.

[0187] (Step ST800: PB) Next, the substrate W is transported to the third heat treatment module PM7 by the fifth transport device HD5, and heat treatment (post-bake) is performed. The post-bake may be performed in an air atmosphere or in a reduced-pressure atmosphere containing N2 or O2. Also, the post-bake may be performed by heating the substrate W to 150°C or higher and 250°C or lower. The post-bake may be performed in the second heat treatment module PM4 instead of the third heat treatment module PM7. In one embodiment, after the post-bake, optical measurement of the substrate W may be performed by the measurement modules PM4PM5. Such measurement may be performed in addition to or instead of the measurement in step ST600. In one embodiment, the control unit CT determines the presence or absence of abnormalities such as defects, scratches, and foreign matter adhesion in the developed pattern of the substrate W based on the appearance, dimensions, and / or pattern shape of the measured substrate W. In one embodiment, when an abnormality is determined in the control unit CT, the substrate W may be reworked or discarded without performing the etching in step ST900. In one embodiment, when an abnormality is determined in the control unit CT, the opening dimension of the resist film on the substrate W may be adjusted using a dry coating unit (CVD device, ALD device, etc.).

[0188] (Process ST900: Etching) After the execution of process ST800, the substrate W is transferred by the fifth transfer device HD5 to the sixth transfer device HD6 of the second carrier station CS2, and is transferred by the sixth transfer device HD6 to the second carrier C2 of the second mounting plate ST2. Thereafter, the second carrier C2 is transferred to a plasma processing system (not shown). The plasma processing system may be, for example, the plasma processing system shown in FIGS. 2 and 3. In the plasma processing system, the underlying film UF of the substrate W is etched using the developed resist film as a mask. Thus, the method MT ends. Note that in process ST700, when developing the resist film using a plasma processing apparatus, the etching may be continuously executed in the plasma processing chamber of the plasma processing apparatus. Further, when the second processing station PS2 includes a plasma processing module in addition to the developing module PM6, the etching may be executed in the plasma processing module. The above-described desorption process may be executed one or more times before or during the etching.

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

[0190] (Appendix 1) A substrate processing method, (a) providing a substrate having an underlying film and a metal-containing resist film on the underlying film on a substrate support portion, 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 of (b) (b1) removing the second region from the first region at a first selection ratio; (b2) further removing the second region from the first region at a second selection ratio different from the first selection ratio, A substrate processing method.

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

[0192] (Appendix 3) The substrate processing method according to Appendix 1 or Appendix 2, wherein the second selectivity is higher than the first selectivity.

[0193] (Appendix 4) In the step (b), the development is performed by wet development, The step (b) is (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 any one of Appendices 1 to 3, satisfying at least one of the above.

[0194] (Appendix 5) In the step (b), the development is performed by dry development in a chamber, The step (b) is (I) The temperature of the substrate support portion in the step (b2) is lower than the temperature of the substrate support portion 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 smaller 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 any one of Appendices 1 to 3, satisfying at least one of the following.

[0195] (Appendix 6) The step (b1) is performed by dry development using a first processing gas containing a first developing gas. The step (b2) is performed by dry development using a second processing gas containing a second developing gas. The step (b) is as follows. (I) The temperature of the substrate support portion in the step (b2) is lower than the temperature of the substrate support portion in the step (b1). (II) The pressure inside the chamber in the step (b2) is lower than the pressure inside the chamber in the step (b1). (III) The acidity of the second developing gas is smaller 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 processing gas contains a protective gas that protects the sidewalls of the first region exposed in the steps (b1) and (b2), and the first processing 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 (in the second processing gas). The substrate processing method according to any one of Appendices 1 to 3, satisfying at least one of the following.

[0196] (Appendix 7) In the step (b), the development is performed by dry development using plasma generated inside the chamber. The step (b) is as follows. (I) The level of the source RF signal power for plasma generation supplied to the chamber in the step (b2) is smaller than the level of the source RF signal power in the step (b1), and (II) The level of the power or voltage of the bias signal supplied to the chamber in the step (b2) is smaller than the level of the power or voltage of the bias signal in the step (b1). The substrate processing method according to any one of Appendices 1 to 3, satisfying at least one of the following.

[0197] (Appendix 8) The substrate processing method according to any one of Appendices 1 to 7, wherein the step (b) further includes a step of modifying the first region between the step (b1) and the step (b2).

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

[0199] (Appendix 10) The substrate processing method according to Appendix 8 or Appendix 9, wherein the step of modifying the first region is performed in the same chamber as the step (b1).

[0200] (Appendix 11) The substrate processing method according to Appendix 8 or Appendix 9, wherein the step of modifying the first region is performed in a chamber different from the step (b1).

[0201] (Appendix 12) The substrate processing method according to any one of Appendices 1 to 3, wherein in the step (b1), the development is performed by wet development, and in the step (b2), the development is performed by dry development.

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

[0203] (Appendix 14) The substrate processing method according to any one of Appendices 1 to 13, wherein the metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0204] (Appendix 15) The substrate processing method according to any one of Appendices 1 to 14, wherein the first region is exposed to EUV light.

[0205] (Appendix 16) The substrate processing method according to any one of Appendices 1 to 15, wherein the switching from the step (b1) to the step (b2) is performed based on the depth or aspect ratio of the opening formed in the metal-containing resist film by the development.

[0206] (Appendix 17) The first region includes a first portion and a second portion on the underlying film below the first portion. The substrate processing method according to any one of Appendices 1 to 16, wherein the step (b1) is performed until immediately before the second portion is exposed or until a part of the second portion is exposed.

[0207] (Appendix 18) (c) After the step (b), the method further includes a step of etching the underlying film using the metal-containing resist film as a mask, according to any one of Appendices 1 to 17.

[0208] (Appendix 19) After the step (b1) and before the step (b2), a step of removing the residue in the first region or the second region generated in the step (b1); and After the step (b2) and before the step (c), a step of removing the residue in the first region or the second region generated in the step (b1) and / or the step (b2); and The substrate processing method according to Appendix 18, further including at least one of the above.

[0209] (Appendix 20) The substrate processing method according to Appendix 18 or Appendix 19, wherein the step (c) is performed in the same chamber as the chamber used in the step (b).

[0210] (Appendix 21) The method for processing a substrate according to appended note 18 or appended note 19, wherein the step (c) is carried out in a chamber different from the chamber used in the step (b).

[0211] (Appended note 22) A method for processing a substrate, comprising: (a) providing a substrate having an underlayer film and a metal-containing resist film formed on the underlayer film on a substrate support portion, wherein the metal-containing resist film has an exposed first region and an unexposed second region; (b) dry-developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film. The step (b) includes: (b1) controlling the temperature of the substrate support portion to a first temperature to remove the second region; (b2) controlling the temperature of the substrate support portion to a second temperature lower than the first temperature to remove the second region. A method for processing a substrate.

[0212] (Appended note 23) The method for processing a substrate according to appended note 22, wherein the step (b) is a step of dry-developing using HBr, the first temperature is 20°C or higher and 60°C or lower, and the second temperature is -20°C or higher and 20°C or lower.

[0213] (Appended note 24) A method for processing a substrate, comprising: (a) providing a substrate having an underlayer film and a metal-containing resist film formed on the underlayer film on a substrate support portion, wherein the metal-containing resist film has an exposed first region and an unexposed second region; (b) dry-developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film. The step (b) includes: (b1) using a first processing gas to remove the second region; (b2) Using a second processing gas having a lower acidity than the first processing gas, removing the second region; and, including Substrate processing method.

[0214] (Appendix 25) The first processing gas includes a halogen-containing inorganic acid, The second processing gas includes an organic acid. The substrate processing method according to Appendix 24.

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

[0216] (Appendix 27) The halogen-containing inorganic acid includes at least one selected from the group consisting of HBr gas, HCl gas, BCl3 gas, HF gas, and HI gas. The substrate processing method according to Appendix 25 or Appendix 26.

[0217] (Appendix 28) The organic acid includes at least one selected from the group consisting of carboxylic acid, β-dicarbonyl compound, and alcohol. The substrate processing method according to any one of Appendix 25 to Appendix 27.

[0218] (Appendix 29) The step (b) is (I) The temperature of the substrate support in the step (b2) is lower than the temperature of the substrate support 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) satisfying at least one of the above. The substrate processing method according to any one of Appendix 24 to Appendix 28.

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

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

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

[0222] (Supplementary Note 33) A substrate processing system having one or more substrate processing apparatuses and a control unit, wherein the control unit is configured to perform, on the one or more substrate processing apparatuses, (a) control to provide a substrate having an underlayer film and a metal-containing resist film on the underlayer film on a substrate support portion, the metal-containing resist film including a first region and a second region, and (b) control to develop the metal-containing resist film to selectively remove the second region from the metal-containing resist film. The control in the step (b) (b1) control to remove the second region from the first region at a first selection ratio, and (b2) control to further remove the second region from the first region at a second selection ratio different from the first selection ratio. 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. Each embodiment can be variously modified without departing from the scope and spirit of the present disclosure. For example, some components in one embodiment can be added to another embodiment. Also, some components in one embodiment can be replaced with corresponding components in another embodiment.

Explanation of Reference Numerals

[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 treatment 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... Underlayer film, W... Substrate

Claims

1. A substrate processing method, comprising: (a) providing a substrate having an underlayer film and a metal-containing resist film on the underlayer film on a substrate support portion, wherein the metal-containing resist film includes 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) includes: (b1) removing the second region with respect to the first region at a first selection ratio; and (b2) further removing the second region with respect to the first region at a second selection ratio different from the first selection ratio. A substrate processing method.

2. The substrate processing method according to claim 1, wherein the first region is an exposed region and the second region is an unexposed region.

3. The substrate processing method according to claim 1, wherein the second selection ratio is higher than the first selection ratio.

4. In the step (b), the development is performed by wet development. The step (b) satisfies at least one of the following conditions: 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). The concentration of the developer used in the step (b2) is lower than the concentration of the developer used in the step (b1). 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.

5. In the step (b), the development is performed by dry development in a chamber. The step (b) satisfies at least one of the following conditions: The temperature of the substrate support portion in the step (b2) is lower than the temperature of the substrate support portion in the step (b1). The pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1). The acidity of the second developing gas used in the step (b2) is smaller than the acidity of the first developing gas used in the step (b1). 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.

6. ​ ​ The step (b1) is performed by dry development using a first processing gas containing a first developing gas. The step (b2) is performed by dry development using a second processing gas containing a second developing gas. The step (b) (I) The temperature of the substrate support portion in the step (b2) is lower than the temperature of the substrate support portion 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 smaller 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 processing gas contains a protective gas that protects the sidewalls of the first region exposed in the steps (b1) and (b2), and the first processing gas either does not contain the protective gas or contains the protective gas at a partial pressure lower than the partial pressure of the protective gas (in the second processing gas). The substrate processing method according to claim 1, satisfying at least one of the above. **Claim 7** In the step (b), the development is performed by dry development using plasma generated in the chamber. The step (b) (I) The level of the source RF signal power for plasma generation supplied to the chamber in the step (b2) is smaller than the level of the source RF signal power in the step (b1), and (II) The level of the power or voltage of the bias signal supplied to the chamber in the step (b2) is smaller than the level of the power or voltage of the bias signal in the step (b1). The substrate processing method according to claim 1, satisfying at least one of the above. **Claim 8** The step (b) further includes a step of modifying the first region between the step (b1) and the step (b2), according to the substrate processing method of claim 1. **Claim 9** The step of modifying the first region includes a step of heating or plasma-treating the substrate, according to the substrate processing method of claim 8. **Claim 10** The step of modifying the first region is performed in the same chamber as the step (b1), according to the substrate processing method of claim 8. **Claim 11** The step of modifying the first region is performed in a chamber different from the step (b1), according to the substrate processing method of claim 8. **Claim 12** In the step (b1), the development is performed by wet development, and in the step (b2), the development is performed by dry development. The substrate processing method according to claim 1.

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

14. The metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti. The substrate processing method according to any one of claims 1 to 13.

15. The first region is exposed to EUV. The substrate processing method according to any one of claims 1 to 13.

16. The switching from the step (b1) to the step (b2) is performed based on the depth or aspect ratio of the opening formed in the metal-containing resist film by the development. The substrate processing method according to any one of claims 1 to 13.

17. The first region includes a first portion and a second portion on the underlying film below the first portion. The step (b1) is performed until immediately before the second portion is exposed, or until a part of the second portion is exposed. The substrate processing method according to any one of claims 1 to 13.

18. (c) After the step (b), further including a step of etching the underlying film using the metal-containing resist film as a mask. The substrate processing method according to any one of claims 1 to 13.

19. After the step (b1) and before the step (b2), a step of removing the residue in the first region or the second region generated in the step (b1); After the step (b2) and before the step (c), a step of removing the residue in the first region or the second region generated in the step (b1) and / or the step (b2); The substrate processing method according to claim 18, further including at least one of the above.

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

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

22. A substrate processing method, Step of providing a substrate having an underlying film and a metal-containing resist film formed on the underlying film on a substrate support, wherein the metal-containing resist film has an exposed first region and an unexposed second region Step (b) of dry-developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film, including The step (b) is Step (b1) of controlling the temperature of the substrate support to a first temperature to remove the second region Step (b2) of controlling the temperature of the substrate support to a second temperature lower than the first temperature to remove the second region, including Substrate processing method

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

24. A substrate processing method, including Step (a) of providing a substrate having an underlying film and a metal-containing resist film formed on the underlying film on a substrate support, wherein the metal-containing resist film has an exposed first region and an unexposed second region Step (b) of dry-developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film, including The step (b) is Step (b1) of using a first processing gas to remove the second region Step (b2) of using a second processing gas having a lower acidity than the first processing gas to remove the second region, including Substrate processing method

25. The first processing gas contains a halogen-containing inorganic acid The second processing gas contains an organic acid The substrate processing method according to claim 24

26. The first processing gas contains a halogen-containing inorganic acid and an organic acid having a lower flow rate than the halogen-containing inorganic acid The second processing gas contains a halogen-containing inorganic acid and an organic acid having a higher flow rate than the halogen-containing inorganic acid The substrate processing method according to claim 24

27. The halogen-containing inorganic acid is at least one selected from the group consisting of HBr gas, HCl gas, BCl ３ gas, and HF gas and HI gas, and the substrate processing method according to claim 25 or claim 26.

28. The organic acid contains at least one selected from the group consisting of carboxylic acid, β-dicarbonyl compound, and alcohol. The substrate processing method according to claim 25 or claim 26

29. The step (b) is (I) The temperature of the substrate support portion in the step (b2) is lower than the temperature of the substrate support portion in the step (b1), and (II) The pressure inside the chamber in the step (b2) is lower than the pressure inside the chamber in the step (b1). The substrate processing method according to claim 24, which satisfies at least one of the above.

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

31. The substrate processing method according to claim 24, wherein in the step (b), after one or more cycles including the steps (b1) and (b2) are performed, the step (b1) is further performed.

32. The step (b) includes a step of removing the second region using plasma generated from the first processing gas and / or the second processing gas after one or more cycles including the steps (b1) and (b2) are performed without using plasma. The substrate processing method according to claim 24.

33. A substrate processing system having one or more substrate processing apparatuses and a control unit, The control unit is configured to control the one or more substrate processing apparatuses to (a) provide a substrate having an underlayer film and a metal-containing resist film on the underlayer film on a substrate support portion, wherein the metal-containing resist film includes 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 in the step (b) is (b1) control to remove the second region from the first region at a first selection ratio; and (b2) control to further remove the second region from the first region at a second selection ratio different from the first selection ratio. A substrate processing system.

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