Apparatus and dry developing method

Abstract

To provide a technique for appropriately dry-developing an exposed metal-containing resist.SOLUTION: A substrate processing method is provided. The substrate processing method includes (a) providing, on a substrate support in a processing chamber, a substrate having an underlying film and a resist film disposed on the underlying film and formed of a metal-containing resist, the metal-containing resist having a first region and a second region. The substrate processing method further includes (b) dry-developing the resist film by supplying a processing gas containing carboxylic acid into the processing chamber, exposing the substrate to the carboxylic acid, and selectively removing the second region with respect to the first region. In (b), a pressure or a partial pressure of the carboxylic acid is 0.3 Torr (40 Pa) or more and less than 100 Torr (13332 Pa).SELECTED DRAWING: Figure 4

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 393,377, entitled "SUBSTRATE TREATMENT METHOD AND SUBSTRATE TREATMENT SYSTEM," filed July 29, 2022, which is incorporated herein by reference in its entirety. [Technical Field]

[0002] SUMMARY Exemplary embodiments of the present disclosure relate to a substrate processing method and a substrate processing system. [Background technology]

[0003] Patent Document 1 discloses a technique for forming a thin film on a semiconductor substrate that is patterned using extreme ultraviolet light (hereinafter referred to as "EUV"). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2021-523403 Summary of the Invention [Problem to be solved by the invention]

[0005] The present disclosure provides techniques for properly dry developing exposed metal-containing resists. [Means for solving the problem]

[0006] In one exemplary embodiment of the present disclosure, a substrate processing method is provided. The substrate processing method includes: (a) providing a substrate on a substrate support in a processing chamber, the substrate having an underlayer and a resist film formed from a metal-containing resist disposed on the underlayer, the metal-containing resist having a first region and a second region; (b) supplying a processing gas containing a carboxylic acid into the processing chamber and exposing the substrate to the carboxylic acid to selectively remove the second region relative to the first region, thereby performing dry development on the resist film; in (b), the pressure or partial pressure of the carboxylic acid is equal to or greater than 0.3 Torr (40 Pa) and less than 100 Torr (13,332 Pa). [Effects of the Invention]

[0007] According to one exemplary embodiment of the present disclosure, a technique for appropriately performing dry development on an exposed metal-containing resist can be provided. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram illustrating an example of the configuration of a heat treatment system. [Figure 2] FIG. 1 is a diagram illustrating an example of the configuration of a plasma processing system. [Figure 3] FIG. 1 is a diagram illustrating an example of the configuration of a capacitively coupled plasma processing apparatus. [Figure 4] 4 is a flowchart showing a substrate processing method according to the first embodiment. [Figure 5] 5 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11 of the substrate processing method shown in FIG. [Figure 6] 1 is a diagram showing an example of an undercoat film UF of a substrate W. FIG. [Figure 7] 1 is a diagram showing an example of an undercoat film UF of a substrate W. FIG. [Figure 8] FIG. 2 is a diagram showing an example of the cross-sectional structure of the substrate W after development. [Figure 9] 10 is a flowchart showing a substrate processing method according to a second embodiment. [Figure 10] Each of (a) of FIG. 10, (b) of FIG. 10, and (c) of FIG. 10 is a timing chart showing an example of the substrate processing method according to the third embodiment. [Figure 11] 10 is a flowchart showing a substrate processing method according to a fourth embodiment. [Figure 12] Each of (a) of FIG. 12 and (b) of FIG. 12 is a diagram showing an example of a cross-sectional structure of the substrate W after processing in step ST42. [Figure 13] Fig. 13(a) is a diagram showing an example of a cross-sectional structure of the substrate W after processing in step ST43, and Fig. 13(b) is a diagram showing an example of a cross-sectional structure of the substrate W after processing in step ST45. [Figure 14] FIG. 14(a) is a schematic cross-sectional view showing another example of the configuration of the heat treatment system, and FIG. 14(b) is a schematic plan view showing another example of the configuration of the heat treatment system. [Figure 15] 3A and 3B are schematic diagrams illustrating an example of the configuration of a substrate support portion. [Figure 16] FIG. 2 is a block diagram for explaining an example of the configuration of a substrate processing system SS. [Figure 17] 1 is a flowchart illustrating a method MT. [Figure 18] Each of (a) and (b) of FIG. 18 shows the results of the experiment. [Figure 19] Each of (a) to (d) of FIG. 19 is a diagram showing the results of the experiment. [Figure 20] FIG. 10 shows the results of an experiment. [Figure 21] FIG. 10 shows the results of an experiment. [Figure 22] FIG. 10 shows the results of an experiment. [Figure 23] Each of (a) to (c) of FIG. 23 is a diagram showing the results of the experiment. [Figure 24] Each of (a) and (b) of FIG. 24 shows the results of the experiment. [Figure 25] FIG. 10 shows the results of an experiment. [Figure 26] FIG. 10 shows the results of an experiment. DETAILED DESCRIPTION OF THE INVENTION

[0009] A substrate processing method according to an exemplary embodiment of the present disclosure includes: (a) providing a substrate on a substrate support in a processing chamber, the substrate having an underlayer and a resist film formed from a metal-containing resist on the underlayer, the metal-containing resist having a first region and a second region; (b) supplying a processing gas containing a carboxylic acid into the processing chamber and exposing the substrate to the carboxylic acid to selectively remove the second region relative to the first region, thereby performing dry development on the resist film; in (b), the pressure or partial pressure of the carboxylic acid is equal to or greater than 0.3 Torr (40 Pa) and less than 100 Torr (13,332 Pa).

[0010] Hereinafter, each embodiment of the present disclosure will be described in detail with reference to the drawings. In each drawing, the same or similar elements are designated by the same reference numerals, and redundant explanations will be omitted. Unless otherwise specified, the positional relationships, such as up, down, left, and right, will be 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.

[0011] <Example of heat treatment system configuration>

[0012] 1 is a diagram illustrating an example of the configuration of a heat treatment system. In one embodiment, the heat treatment system includes a heat treatment apparatus 100 and a control unit 200. The heat treatment system is an example of a substrate treatment system, and the heat treatment apparatus 100 is an example of a substrate treatment apparatus.

[0013] The heat treatment apparatus 100 has a process chamber 102 that can be sealed. The process chamber 102 is, for example, an airtight cylindrical container, and is configured so that the internal atmosphere can be adjusted. A side wall heater 104 is provided on the side wall of the process chamber 102. A ceiling heater 130 is provided on the ceiling wall (top plate) of the process chamber 102. A ceiling surface 140 of the ceiling wall (top plate) of the process chamber 102 is formed as a horizontal, flat surface, and its temperature is adjusted by the ceiling heater 130.

[0014] A substrate support 121 is provided at the lower side of the processing chamber 102. The substrate support 121 constitutes a mounting portion on which the substrate W is mounted. The substrate support 121 is formed, for example, in a circular shape in a plan view, and the substrate W is mounted on its horizontally formed surface (top surface). A stage heater 120 is embedded within the substrate support 121. This stage heater 120 can heat the substrate W mounted on the substrate support 121. A ring assembly (not shown) may be disposed in the substrate support 121 to surround the substrate W. The ring assembly may include one or more annular members. By disposing the ring assembly around the substrate W, temperature controllability in the outer peripheral region of the substrate W can be improved. The ring assembly may be made of an inorganic material or an organic material depending on the desired heat treatment.

[0015] The substrate support 121 is supported within the processing chamber 102 by support columns 122 provided on the bottom surface of the processing chamber 102. A plurality of lift pins 123 that can be raised and lowered vertically are provided on the circumferential outer sides of the support columns 122. Each of the lift pins 123 is inserted into a through-hole provided in the substrate support 121. The lift pins 123 are arranged at intervals in the circumferential direction. The lift pins 123 are raised and lowered by a lift mechanism 124. When the lift pins 123 protrude from the surface of the substrate support 121, the substrate W can be transferred between a transport mechanism (not shown) and the substrate support 121.

[0016] An exhaust port 131 having an opening is provided in the sidewall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump, a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. The pressure inside the processing chamber 102 is adjusted by adjusting the exhaust flow rate, etc., using the exhaust mechanism 132. Note that a transfer port for a substrate W (not shown) that can be opened and closed is formed in the sidewall of the processing chamber 102 at a position different from the position where the exhaust port 131 opens.

[0017] Furthermore, a gas nozzle 141 is provided on the sidewall of the processing chamber 102 at a position different from the exhaust port 131 and the transfer port for the substrate W. The gas nozzle 141 supplies processing gas into the processing chamber 102. The gas nozzle 141 is provided on the sidewall of the processing chamber 102 on the opposite side from the exhaust port 131 when viewed from the center of the substrate support 121. That is, the gas nozzle 141 is provided on the sidewall of the processing chamber 102 symmetrically to the exhaust port 131 with respect to a vertical imaginary plane that passes through the center of the substrate support 121.

[0018] The gas nozzle 141 is formed in a rod shape that protrudes from the sidewall of the processing chamber 102 toward the center of the processing chamber 102. The tip of the gas nozzle 141 extends, for example, horizontally from the sidewall of the processing chamber 102. The processing gas is discharged into the processing chamber 102 from a discharge port that opens at the tip of the gas nozzle 141, flows in the direction of the dashed-dotted arrow shown in FIG. 1 , and is exhausted from the exhaust port 131. The tip of the gas nozzle 141 may have a shape that extends obliquely downward toward the substrate W, or may have a shape that extends obliquely upward toward the ceiling surface 140 of the processing chamber 102.

[0019] The gas nozzle 141 may be provided, for example, in the ceiling wall of the processing chamber 102. The exhaust port 131 may be provided in the bottom surface of the processing chamber 102.

[0020] The heat treatment apparatus 100 has a gas supply pipe 152 connected to a gas nozzle 141 from outside the processing chamber 102. A piping heater 160 for heating the gas in the gas supply pipe 152 is provided around the gas supply pipe 152. The gas supply pipe 152 is connected to a gas supply unit 170. The gas supply unit 170 includes at least one gas source and at least one flow rate controller. The gas supply unit may include a vaporizer that vaporizes a liquid material.

[0021] The control unit 200 processes computer-executable instructions that cause the heat treatment apparatus 100 to perform the various steps described in this disclosure. The control unit 200 may be configured to control each element of the heat treatment apparatus 100 to perform the various steps 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 implemented, for example, by the computer 200a. The processing unit 200a1 may be configured to read a program from the storage unit 200a2 and execute the read program to perform various control operations. This program may be stored in the storage unit 200a2 in advance or may be acquired via a medium when needed. 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 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 device 100 via a communication line such as a LAN (Local Area Network).

[0022] <Configuration example of plasma processing system>

[0023] FIG. 2 is a diagram illustrating an example of the configuration of a plasma processing system used as a development processing system. In one embodiment, the plasma processing system includes a plasma processing device 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing device 1 is an example of a substrate processing device. The plasma processing device 1 includes a plasma processing chamber (hereinafter simply referred to as a "processing chamber") 10, a substrate support 11, and a plasma generation unit 12. The plasma processing chamber 10 has a plasma processing space. The plasma processing chamber 10 also has at least one gas supply port for supplying at least one processing gas to the plasma processing space and at least one gas exhaust port for exhausting gas from the plasma processing space. The gas supply port is connected to a gas supply unit 20 (described later), and the gas exhaust port is connected to an exhaust system 40 (described later). The substrate support 11 is disposed in the plasma processing space and has a substrate support surface for supporting a substrate.

[0024] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be capacitively coupled plasma (CCP), inductively coupled plasma (ICP), electron-cyclotron-resonance plasma (ECR plasma), helicon wave plasma (HWP), or surface wave plasma (SWP). Various types of plasma generating units may be used, including alternating current (AC) plasma generating units and direct current (DC) plasma generating units. In one embodiment, the AC signal (AC power) used in the AC plasma generating unit has a frequency in the range of 100 kHz to 10 GHz. Therefore, the AC signal includes a radio frequency (RF) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0025] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various steps described in this disclosure. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to perform the various steps described herein. In one embodiment, some 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 memory unit 2a2, and a communication interface 2a3. Each component of the control unit 2 may be similar to each component of the control unit 200 (see FIG. 1) described above.

[0026] The following describes a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1. Fig. 3 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0027] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply 20, a power supply 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support 11 and a gas inlet. The gas inlet is configured to introduce at least one process gas into the plasma processing chamber 10. The gas inlet includes a showerhead 13. The substrate support 11 is disposed within the plasma processing chamber 10. The showerhead 13 is disposed above the substrate support 11. In one embodiment, the showerhead 13 forms at least a portion 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, a sidewall 10a of the plasma processing chamber 10, and the substrate support 11. The plasma processing chamber 10 is grounded. The showerhead 13 and the substrate support 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0028] The substrate support 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central region 111a for supporting a substrate W and an annular region 111b for supporting the ring assembly 112. A wafer is an example of a substrate W. The annular region 111b of the main body 111 surrounds the central region 111a of the main body 111 in a plan view. The substrate W is disposed on the central region 111a of the main body 111, and the ring assembly 112 is disposed on the annular region 111b of the main body 111 so as to surround the substrate W on the central region 111a of the main body 111. Therefore, the central region 111a is also called a substrate support surface for supporting the substrate W, and the annular region 111b is also called a ring support surface for supporting the ring assembly 112.

[0029] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive member. The conductive member of the base 1110 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 within the ceramic member 1111a. The ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that the annular region 111b may also be provided by another member surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member. 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. Furthermore, at least one RF / DC electrode coupled to an RF power supply 31 and / or a DC power supply 32, which will be described later, may be disposed within the ceramic member 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or a DC signal, which will be described later, is supplied to the at least one RF / DC electrode, the RF / DC electrode is also called a bias electrode. Note that the conductive member of the base 1110 and the at least one RF / DC electrode may function as multiple lower electrodes. Alternatively, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support 11 includes at least one lower electrode.

[0030] The ring assembly 112 includes one or more annular members. In one embodiment, the one or more annular members include one or more edge rings and at least one cover ring. The edge rings are formed of a conductive or insulating material, and the cover rings are formed of an insulating material.

[0031] The substrate support 11 may also include a temperature adjustment module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature adjustment module may include a heater, a heat transfer medium, a flow passage 1110a, or a combination thereof. A heat transfer fluid such as brine or a gas flows through the flow passage 1110a. In one embodiment, the flow passage 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111. The substrate support 11 may also include a heat transfer gas supply configured to supply a heat transfer gas to a gap between the backside of the substrate W and the central region 111a.

[0032] The showerhead 13 is configured to introduce at least one processing gas from the gas supply unit 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and multiple gas inlets 13c. The processing gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the multiple gas inlets 13c. The showerhead 13 also includes at least one upper electrode. In addition to the showerhead 13, the gas introduction unit may also include one or more side gas injectors (SGIs) attached to one or more openings formed in the sidewall 10a.

[0033] 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 a corresponding gas source 21 to the showerhead 13 via a corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Additionally, the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of the at least one process gas.

[0034] 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. This generates a plasma from at least one processing gas supplied to the plasma processing space 10s. Therefore, the RF power supply 31 can function as at least a part of the plasma generation unit 12. Furthermore, by supplying a bias RF signal to the at least one lower electrode, a bias potential is generated on the substrate W, and ion components in the formed plasma can be attracted to the substrate W.

[0035] In one embodiment, the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b. The first RF generating unit 31a is coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit and is configured to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generating unit 31a may be configured to generate multiple 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.

[0036] The second RF generating unit 31b is coupled to at least one lower electrode via at least one impedance matching circuit and configured to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF generating unit 31b may be configured to generate multiple bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. In various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0037] The power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generator 32a and a second DC generator 32b. In one embodiment, the first DC generator 32a is connected to at least one lower electrode and configured to generate a first DC signal. The generated first DC signal is applied to the at least one lower electrode. In one embodiment, the second DC generator 32b is connected to at least one upper electrode and configured to generate a second DC signal. The generated second DC signal is applied to the at least one upper electrode.

[0038] In various embodiments, the first and second DC signals may be pulsed. In this case, a sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulses may have a rectangular, trapezoidal, triangular, or combination thereof. In one embodiment, a waveform generator for generating a sequence of voltage pulses from the DC signal is connected between the first DC generator 32a and at least one lower electrode. Thus, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. When the second DC generator 32b and the waveform generator constitute a voltage pulse generator, the voltage pulse generator is connected to at least one upper electrode. The voltage pulses may have either positive or negative polarity. Furthermore, the sequence of voltage pulses may include one or more positive voltage pulses and one or more negative voltage pulses within one period. The first and second DC generating units 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generating unit 32a may be provided instead of the second RF generating unit 31b.

[0039] The exhaust system 40 may be connected to, for example, a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure regulating valve regulates the pressure in the plasma processing space 10s. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0040] <Substrate processing method>

[0041] Various embodiments of the substrate processing method according to the present disclosure will be described below.

[0042] [First embodiment]

[0043] 4 is a flowchart showing a substrate processing method according to a first embodiment (hereinafter also referred to as "method MT1"). As shown in FIG. 4, method MT1 includes a step ST11 of providing a substrate and a step ST12 of developing the substrate. In one embodiment, the development process in step ST12 is performed by a dry process using a processing gas (hereinafter also referred to as "dry development").

[0044] The method MT1 may be performed using any one of the substrate processing systems described above (see FIGS. 1 to 3), or may be performed using two or more of these substrate processing systems. For example, the method MT1 may be performed in a heat treatment system (see FIG. 1). Below, the method MT1 will be described using an example in which the control unit 200 controls each unit of the heat treatment apparatus 100 to apply the method MT1 to the substrate W.

[0045] (Process ST11: Providing the substrate)

[0046] First, in step ST11, a substrate W is provided in the processing chamber 102 of the heat treatment apparatus 100. The substrate W is provided on the substrate support 121 via lift pins 123. After the substrate W is placed on the substrate support 121, the temperature of the substrate support 121 is adjusted to a set temperature. The temperature adjustment of the substrate support 121 may be performed by controlling the output of one or more heaters selected from the sidewall heater 104, the stage heater 120, the ceiling heater 130, and the piping heater 160 (hereinafter collectively referred to as "each heater"). In method MT1, the temperature of the substrate support 121 may be adjusted to the set temperature before step ST11. That is, the substrate W may be provided on the substrate support 121 after the temperature of the substrate support 121 is adjusted to the set temperature.

[0047] 5 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11 of the substrate processing method shown in FIG. The substrate W includes an underlayer UF and a resist film RM formed on the underlayer UF. The substrate W may be used in the manufacture of semiconductor devices. Semiconductor devices include, for example, memory devices such as DRAMs and 3D-NAND flash memories, and logic devices.

[0048] The resist film RM is a metal-containing resist film containing a metal. For example, the metal may include at least one metal selected from the group consisting of Sn, Hf, and Ti. For example, the resist film RM contains Sn and may include tin oxide (SnO bond) and tin hydroxide (Sn—OH bond). The resist film RM may further include an organic material.

[0049] 5, the resist film RM has an exposed first region RM1 and an unexposed second region RM2. The first region RM1 is an area exposed to EUV light, i.e., an EUV-exposed region. The second region RM2 is an area not exposed to EUV light, i.e., an unexposed region.

[0050] The undercoat film UF may be an organic film, a dielectric film, a metal film, a semiconductor film, or a laminated film of these formed on a silicon wafer.

[0051] 6 and 7 are diagrams showing examples of an undercoat film UF of a substrate W. As shown in Fig. 6, the undercoat film UF may be composed of a first film UF1, a second film UF2, and a third film UF3. As shown in Fig. 7, the undercoat film UF may be composed of a second film UF2 and a third film UF3.

[0052] The first film UF1 is, for example, a spin-on-glass (SOG) film, a SiC film, a SiON film, a Si-containing anti-reflective coating (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 multiple types of stacked silicon-containing films. For example, the third film UF3 may be composed of alternately stacked silicon oxide films and silicon nitride films. The third film UF3 may also be composed of alternately stacked silicon oxide films and polycrystalline silicon films. The third film UF3 may also be a stacked film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. The third film UF3 may also be composed of stacked silicon oxide films and silicon carbonitride films. The third film UF3 may also be a laminated film including a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.

[0053] In one embodiment, the substrate W is formed as follows. First, a metal-containing photoresist film is formed on an underlayer film that has been subjected to adhesion improvement treatment, etc. The film formation may be performed by a dry process, a wet process such as a solution coating method, or both a dry process and a wet process. Note that a surface modification process may be performed on the underlayer film before the photoresist film is formed. After the photoresist film is formed, the substrate is subjected to a heat treatment, i.e., a pre-bake (Post Apply Bake: PAB). The pre-bake substrate may be subjected to an additional heat treatment. After the heat treatment, the substrate is transferred to an exposure tool, and EUV light is irradiated onto the photoresist film through an exposure mask (reticle). This forms 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. The first region RM1 corresponds to an opening formed in the exposure mask (reticle). The second region RM2 corresponds to a pattern formed in the exposure mask (reticle). The EUV light has a wavelength in the range of 10 to 20 nm, for example. 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. After exposure, the substrate W is transported from the exposure apparatus to a heat treatment apparatus under controlled atmosphere, and is subjected to a heat treatment, i.e., a post-exposure bake (PEB). The substrate W after the PEB may be subjected to an additional heat treatment.

[0054] (Step ST12: Developing the substrate)

[0055] Next, in step ST12, the substrate W is exposed to a processing gas, whereby the second region RM2 of the substrate W is selectively removed, and the resist film RM is developed.

[0056] In step ST12, a process gas is supplied into the process chamber 102 through the gas nozzle 141. In one embodiment, the process gas includes a carboxylic acid. In one embodiment, the carboxylic acid may be formic acid (HCOOH). In one embodiment, the carboxylic acid may be acetic acid (CHCOOH). In one embodiment, the carboxylic acid may include a halogen element, and the halogen element may include fluorine and / or chlorine. The carboxylic acid containing fluorine may be, for example, at least one selected from the group consisting of monofluoroacetic acid (CFHCOOH), difluoroacetic acid (CFHCOOH), and trifluoroacetic acid (CFCOOH), or may be trifluoroacetic acid. The carboxylic acid containing chlorine may be, for example, at least one selected from the group consisting of monochloroacetic acid (CClHCOOH), dichloroacetic acid (CClHCOOH), and trifluoroacetic acid (CClCOOH). The carboxylic acid containing fluorine and chlorine may be, for example, chlorofluoroacetic acid. In one embodiment, the carboxylic acid may be at least one selected from the group consisting of formic acid, acetic acid, and trifluoroacetic acid, may be formic acid and / or trifluoroacetic acid, or may be trifluoroacetic acid.

[0057] The processing gas may further include an inert gas. The inert gas may be nitrogen gas or a noble gas such as Ar. In addition to the inert gas, the processing gas may further include an inorganic acid or an organic acid other than a carboxylic acid. In addition, the processing gas may include an oxidizing gas such as O gas and / or CO gas.

[0058] Furthermore, in step ST12, the pressure of the process gas in the process chamber 102 is adjusted. More specifically, the pressure of the carboxylic acid in the process gas is adjusted. When the process gas contains only the carboxylic acid, i.e., when the process gas is a single gas, the pressure of the carboxylic acid in the process gas is the pressure of the process gas. When the process gas is a mixed gas containing the carboxylic acid and a gas other than the carboxylic acid, the pressure of the carboxylic acid in the process gas is the partial pressure of the carboxylic acid in the process gas. Hereinafter, the pressure of the process gas when the process gas is a single gas and the partial pressure of the carboxylic acid in the process gas when the process gas is a mixed gas may be referred to as the "carboxylic acid pressure." The pressure of the carboxylic acid can be adjusted by the flow rate of the carboxylic acid supplied into the process chamber 102 and / or the flow rate of the carboxylic acid exhausted from the process chamber 102. When the process gas is a mixed gas, the pressure of the carboxylic acid can be adjusted by the flow rate of the carboxylic acid gas and the flow rate of the gas other than the carboxylic acid supplied into the process chamber 102 and / or the flow rate of the carboxylic acid gas and the gas other than the carboxylic acid exhausted from the process chamber 102.

[0059] In one embodiment, the partial pressure of the carboxylic acid in step ST12 may be 0.3 Torr (40 Pa) or more, 0.5 Torr (66.6 Pa) or more, 1 Torr (133 Pa) or more, 1.5 Torr (200 Pa) or more, 2 Torr (266 Pa) or more, or 5 Torr (666 Pa) or more. The partial pressure of the carboxylic acid may be less than 100 Torr (13332 Pa), 90 Torr (12000 Pa) or less, 80 Torr (13332 Pa) or less, 70 Torr (9333 Pa) or less, 60 Torr (8000 Pa) or less, or 10 Torr (1333 Pa) or less. In one embodiment, the pressure of the carboxylic acid may be 1 Torr or more and less than 100 Torr. When the pressure of the carboxylic acid is 1 Torr or more, a higher development rate and a higher throughput can be achieved. On the other hand, if the pressure of the carboxylic acid is less than 100 Torr, a higher development contrast (selectivity) can be achieved along with a high development rate.

[0060] Furthermore, in step ST12, the temperature of the substrate W or the substrate support 121 can be controlled. In one embodiment, the temperature of the substrate support 121 in step ST12 may be −20° C. or higher, 0° C. or higher, 20° C. or higher, 90° C. or higher, or 120° C. or higher. The temperature of the substrate support 121 in step ST12 may be 300° C. or lower, 220° C. or lower, 210° C. or lower, or 200° C. or lower. In one embodiment, the temperature of the substrate support 121 is controlled to be −20° C. or higher and 220° C. or lower. If the temperature of the substrate support 121 is 0° C. or higher, a decrease in the development rate can be suppressed. On the other hand, if the temperature of the substrate support 121 is lower than 200° C., a high development rate and a high development contrast (selectivity) can be achieved. The temperature of the substrate support 121 can be controlled by the power supplied to the stage heater 120. The temperature of the substrate support 121 may be controlled by power supplied to the sidewall heater 104 and / or the ceiling heater 130, in addition to or instead of the stage heater 120. The temperature of the substrate support 121 may be controlled by an infrared lamp, a microwave, or the like, in addition to or instead of the power supplied to each of the heaters described above.

[0061] In step ST12, when the carboxylic acid in the process gas is formic acid, the temperature of the substrate support 121 may be 120°C or higher. In step ST12, when the carboxylic acid in the process gas is formic acid, the pressure of the carboxylic acid may be 0.3 Torr or higher, or 0.5 Torr or higher. In step ST12, when the carboxylic acid in the process gas is trifluoroacetic acid, the temperature of the substrate support 121 may be 90°C or higher, or 120°C or higher. In step ST12, when the carboxylic acid in the process gas is trifluoroacetic acid, the pressure of the carboxylic acid may be 0.3 Torr or higher, or 0.5 Torr or higher. In step ST12, when the carboxylic acid in the process gas is acetic acid, the temperature of the substrate support 121 may be 120°C or higher, 150°C or higher, or 180°C or higher. In step ST12, when the carboxylic acid in the process gas is acetic acid, the pressure of the carboxylic acid may be 0.3 Torr or higher, or 0.5 Torr or higher.

[0062] Step ST12 may be performed until the second region RM2 is removed and the base film UF is exposed. FIG. 8 is a diagram showing an example of the cross-sectional structure of the substrate W after development. In the example shown in FIG. 8, 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 base film UF surrounded by the side surface. The opening OP has a shape corresponding to the second region RM2 in a plan view of the substrate W (and consequently a shape corresponding to the exposure mask pattern used for EUV exposure). The shape may be, for example, a circle, an ellipse, a rectangle, a line, or a combination of one or more of these. The resist film RM after development may have multiple openings OP. The multiple openings OP may each have a linear shape and be arranged at regular intervals to form a line-and-space pattern. Alternatively, the multiple openings OP may be arranged in a lattice pattern to form a pillar pattern.

[0063] According to the first embodiment, the second region RM2 can be removed with a high selectivity (the ratio of the development rate of the second region RM2 to the development rate of the first region RM1, hereinafter also referred to as "development contrast") relative to the first region RM1. Furthermore, according to the first embodiment, the generation of residues due to development can be suppressed.

[0064] Next, a substrate processing method according to another embodiment of the present disclosure will be described. Note that, in the following, parts that overlap with the first embodiment will be explained briefly or omitted.

[0065] [Second embodiment]

[0066] 9 is a flowchart showing a substrate processing method according to a second embodiment (hereinafter also referred to as "method MT2"). Method MT2 includes steps ST21 and ST22. In step ST21, a substrate W is provided, similar to step ST11 of method MT1. In the subsequent step ST22, the resist film RM is developed. Step ST22 includes step ST22-1 of developing a portion of the resist film under first conditions and step ST22-2 of developing the resist film RM under second conditions different from the first conditions.

[0067] In one embodiment, the combination of the first condition and the second condition may satisfy one or more of the following conditions (A) to (C), or may satisfy two or more of them: In the following description, the pressure of the carboxylic acid refers to the pressure of the carboxylic acid when the processing gas is a single gas, and refers to the partial pressure of the carboxylic acid when the processing gas is a mixed gas.

[0068] (A) In step ST22-1, the resist film RM is developed using a first process gas, and in step ST22-2, the resist film RM is developed using a second process gas different from the first process gas. (B) In step ST22-1, the pressure of the carboxylic acid is set to a first pressure to develop the resist film RM, and in step ST22-2, the pressure of the carboxylic acid is set to a second pressure different from the first pressure to develop the resist film RM. (C) In step ST22-1, the substrate support part 121 is set to a first temperature to develop the resist film RM, and in step ST22-2, the substrate support part 121 is set to a second temperature different from the first temperature to develop the resist film RM.

[0069] In one example that satisfies condition (A), a gas containing an inorganic acid may be used as the first process gas, and a gas containing a carboxylic acid may be used as the second process gas. The inorganic acid may be a gas that is more acidic than the carboxylic acid. The inorganic acid may be, for example, at least one selected from the group consisting of HBr, BCl3, HCl, HF, and HI. The carboxylic acid may be one or more of the carboxylic acids described above.

[0070] In another example that satisfies condition (A), a gas containing an organic acid other than a carboxylic acid may be used as the first process gas, and a gas containing a carboxylic acid may be used as the second process gas. Alternatively, a gas containing a carboxylic acid may be used as the first process gas, and a gas containing an organic acid other than a carboxylic acid may be used as the second process gas. Alternatively, a gas containing a carboxylic acid may be used as the first process gas, and a gas containing a carboxylic acid or an organic acid other than a carboxylic acid, which has an acidity lower than that of the first process gas, may be used as the second process gas. The organic acid other than a carboxylic acid may be a β-dicarbonyl compound such as acetylacetone (CHC(O)CHC(O)CH), trichloroacetylacetone (CClC(O)CHC(O)CH), hexachloroacetylacetone (CClC(O)CHC(O)CCl), trifluoroacetylacetone (CFC(O)CHC(O)CH), or hexafluoroacetylacetone (HFAc, CFC(O)CHC(O)CF), or an alcohol such as nonafluoro-tert-butyl alcohol ((CF)C—OH). The carboxylic acid may be any one or more of the carboxylic acids described above.

[0071] In another example that satisfies condition (A), a gas containing a first carboxylic acid may be used as the first process gas, and a gas containing a second carboxylic acid different from the first carboxylic acid may be used as the second process gas. The acidity of the second carboxylic acid may be lower than the acidity of the first carboxylic acid. Trifluoroacetic acid may be used as the first carboxylic acid, and formic acid or acetic acid may be used as the second carboxylic acid. Alternatively, formic acid may be used as the first carboxylic acid, and acetic acid may be used as the second carboxylic acid.

[0072] In an example that satisfies condition (B), a mixed gas containing a carboxylic acid may be used as the processing gas. For example, the processing gas may contain a carboxylic acid and an inert gas. In this case, the partial pressure of the carboxylic acid may be set to a first pressure in step ST22-1, and the partial pressure of the carboxylic acid may be set to a second pressure different from the first pressure in step ST22-2. The second pressure may be lower than the first pressure. In one example, the first pressure may be 60 Torr or more and 90 Torr or less, and the second pressure may be 1.5 Torr or more and 20 Torr or less.

[0073] In another example that satisfies condition (B), the process gas contains a carboxylic acid and an inorganic acid such as HBr. In this case, the partial pressure of the carboxylic acid may be set to a first pressure in step ST22-1, and the partial pressure of the carboxylic acid may be set to a second pressure different from the first pressure in step ST22-2. The second pressure may be higher than the first pressure. In one example, the first pressure may be equal to or higher than 30 Torr and equal to or lower than 50 Torr, and the second pressure may be equal to or higher than 80 Torr and equal to or lower than 90 Torr.

[0074] In an example that satisfies condition (C), the second temperature may be lower than the first temperature. In one example, the first temperature may be 110°C or higher and 130°C or lower, and the second temperature may be 70°C or higher and 90°C or lower.

[0075] According to method MT2, the development conditions are changed depending on the development depth of the resist film RM. Therefore, even if the intensity of the exposure reaction differs in the thickness direction, the second region RM2 can be removed with a high selectivity relative to the first region RM1. The change from the first conditions to the second conditions may be continuous or stepwise. Furthermore, a cycle including steps ST22-1 and ST22-2 may be repeated multiple times.

[0076] [Third embodiment]

[0077] 10(a), 10(b), and 10(c) are timing charts illustrating an example of a substrate processing method according to a third embodiment (hereinafter also referred to as "method MT3"). Method MT3 includes steps ST31 and ST32. In step ST31, a substrate W is provided, similar to step ST11 in method MT1. In the subsequent step ST32, the resist film RM is developed. As shown in FIGS. 10(a), 10(b), and 10(c), the period during which step ST32 is performed includes a first period and second periods alternating with the first period.

[0078] In one embodiment, the combination of the treatment conditions for the first period and the treatment conditions for the second period may satisfy one or more of the following conditions (A) to (C), or may satisfy two or more of them: In the following description, the pressure of the carboxylic acid refers to the pressure of the carboxylic acid when the treatment gas is a single gas, and refers to the partial pressure of the carboxylic acid when the treatment gas is a mixed gas.

[0079] (A) In a first period, the resist film RM is developed using a first processing gas, and in a second period, the resist film RM is developed using a second processing gas different from the first processing gas (see (a) of FIG. 10). (B) In a first period, the pressure of the carboxylic acid is set to a first pressure to develop the resist film RM, and in a second period, the pressure of the carboxylic acid is set to a second pressure different from the first pressure to develop the resist film RM (see (b) of Figure 10). (C) In a first period, the temperature of the substrate support part 121 is set to a first temperature to develop the resist film RM, and in a second period, the temperature of the substrate support part 121 is set to a second temperature different from the first temperature to develop the resist film RM (see (c) of Figure 10).

[0080] In one example that satisfies condition (A), a gas containing an inorganic acid may be used as the first process gas, and a gas containing a carboxylic acid may be used as the second process gas. The inorganic acid may be, for example, at least one selected from the group consisting of HBr, BCl3, HCl, and HF. The carboxylic acid may be one or more of the carboxylic acids described above.

[0081] In another example that satisfies condition (A), a gas containing an organic acid other than a carboxylic acid may be used as the first process gas, and a gas containing a carboxylic acid may be used as the second process gas. Alternatively, a gas containing a carboxylic acid may be used as the first process gas, and a gas containing an organic acid other than a carboxylic acid may be used as the second process gas. The gas containing an organic acid other than a carboxylic acid may be, for example, the above-mentioned β-dicarbonyl compound or alcohol. The carboxylic acid may be one or more of the above-mentioned carboxylic acids.

[0082] In another example that satisfies condition (A), a gas containing a first carboxylic acid may be used as the first process gas, and a gas containing a second carboxylic acid different from the first carboxylic acid may be used as the second process gas. The first carboxylic acid and the second carboxylic acid may each be one or more of the carboxylic acids described above.

[0083] In one example that satisfies condition (B), the first pressure may be equal to or greater than 0 Torr and equal to or less than 0.1 Torr, and the second pressure may be equal to or greater than 1 Torr and equal to or less than 10 Torr.

[0084] In one example that satisfies condition (C), the first temperature may be 110°C or higher and 130°C or lower, and the second temperature may be 170°C or higher and 190°C or lower.

[0085] According to method MT3, the developing step (ST32) includes a first period and a second period alternating with the first period. This promotes volatilization of reaction by-products generated in step ST32, thereby suppressing the generation of residues in step ST32. Note that in the timing charts shown in Figures 10(b) and 10(c), the pressure of the carboxylic acid and the temperature of the substrate support 121 are both controlled to be "Low" in the first period and "High" in the second period. However, they may also be controlled to be "High" in the first period and "Low" in the second period.

[0086] [Fourth embodiment]

[0087] 11 is a flowchart showing a substrate processing method according to a fourth embodiment (hereinafter also referred to as "method MT4"). The method MT4 includes a step of providing a substrate W (step ST41), a step of removing a part of the second region (step ST42), a step of forming a deposition film (step ST43), a descum step (step ST44), and a step of removing the second region (step ST45).

[0088] In method MT4, the plasma processing apparatus 1 shown in Fig. 3 may be used as the development processing system. In method MT4, the thermal processing apparatus 100 as shown in Fig. 1 may also be used, in which case the processing chamber 102 may be configured to include a plasma supply unit (not shown) capable of supplying plasma generated outside the processing chamber 102 into the processing chamber 102. Below, method MT4 will be described using the case where the plasma processing system shown in Fig. 3 is used as the development processing system, as an example.

[0089] (Process ST41~ST42)

[0090] In step ST41, a substrate W is provided in the same manner as in step ST11. In the subsequent step ST42, the resist film RM is developed to remove a portion of the second region RM2. In step ST42, development may be stopped before the base film UF is exposed. The portion of the second region RM2 may be removed by a process similar to that of step ST12 described above. The process gas used in step ST42 is the same as that used in step ST11. Each of FIGS. 12(a) and 12(b) shows an example of the cross-sectional structure of the substrate W after step ST42. In the example shown in FIG. 12(b), residues (scum) S1 to S3 remain that cannot be completely removed by the process of step ST42. The scum S1 to S3 can be removed in step ST44 (a descum process) described later.

[0091] (Process ST43)

[0092] In step ST43, a deposited film DF is formed. The deposited film DF may be a carbon-containing film or a silicon-containing film. The deposited film DF may be formed by plasma generated from a third process gas containing a carbon-containing gas or a silicon-containing gas. In one example, first, a third process gas is supplied from the gas supply unit 20 into the plasma processing space 10s. Next, a source RF signal is supplied to the upper electrode or the lower electrode. This generates a high-frequency electric field in the plasma processing space 10s, and plasma is generated from the third process gas. Then, radicals containing carbon or silicon contained in the plasma may be deposited on at least a portion of the resist film RM.

[0093] 13A is a diagram showing an example of the cross-sectional structure of the substrate W after step ST43. As shown in FIG. 13A, the deposited film DF is formed on the upper surface TS1 of the first region RM1 of the resist film RM (hereinafter, the "first region RM1 of the resist film RM" will also be referred to as the "first region RM1"). The deposited film DF may be further formed on at least a part of the side surface SS1 of the first region RM1. In this case, the deposited film DF may be formed thicker on the upper surface TS1 than on the side surface SS1 of the first region RM1. The deposited film DF may also be deposited on at least a part of the upper surface TS2 of the second region RM2. The deposited film DF may be formed in a portion of the upper surface TS2 of the second region RM2 where the space provided by the first region RM1 on the upper surface TS1 is larger. The deposited film DF may be formed thicker on the upper surface TS1 of the first region RM1 than on the upper surface TS2 of the second region RM2.

[0094] When a carbon-containing film is formed as the deposition film DF, the third process gas may contain a gas containing carbon and hydrogen. x H y The gas may be a fluorocarbon (CxFz: x and z are positive integers. Also called a CF-based gas), and for example, may be C4F6 or C4F8. The gas may be a hydrofluorocarbon (C x H y F z (x, y, and z are positive integers. Also called CHF-based gas.) and, for example, may be CH2F2 gas or CH3F gas.

[0095] On the other hand, when a silicon-containing film is formed as the deposited film DF, the third process gas may be, for example, a mixed gas of a silicon-containing gas, such as SiCl4 gas or SiF4 gas, and an oxidizing gas or a hydrogen-containing gas. The oxidizing gas may be, for example, at least one gas selected from the group consisting of O2 gas, CO gas, and CO2 gas. The hydrogen-containing gas may be, for example, H2 gas. The deposited film DF may be formed by atomic layer deposition (hereinafter also referred to as "ALD"). For example, when a silicon-containing film is formed as the deposited film DF, the above-mentioned silicon-containing gas may be supplied as a precursor to form a precursor layer on the upper surface TS1 of the first region RM1, and then an oxidizing gas or a hydrogen-containing gas may be supplied to react with the precursor layer.

[0096] In one embodiment, a silicon-containing film may be formed as the deposited film DF, and then a carbon-containing film may be formed. In this case, step ST44, which will be described later, may be performed simultaneously with the formation of the carbon-containing film. In one embodiment, a carbon-containing film may be formed as the deposited film DF, and then a silicon-containing film may be formed. In this case, step ST44, which will be described later, may be performed simultaneously with the formation of the silicon-containing film. Note that in step ST43, a bias signal (bias RF signal or pulsed first DC signal) does not need to be supplied to the lower electrode of the substrate support 11.

[0097] (Process ST44)

[0098] As described above, if scum is generated in step ST42, a descum step (step ST44) may be performed to remove the scum. As shown in FIG. 12(b), the scum may include scum S1 formed on the sidewall of the first region RM1, scum S2 extending from the lower portion of the exposed portion of the first region RM1 toward the surface of the second region RM2, and scum S3 formed on the surface of the second region RM2. In step ST44, the scum S1 to S3 may be removed by plasma generated from a fourth process gas. For example, first, a fourth process gas is supplied from the gas supply unit 20 into the plasma processing space 10s. Next, a source RF signal is supplied to the upper electrode or the lower electrode. This generates a high-frequency electric field in the plasma processing space 10s, and plasma is generated from the fourth process gas. At this time, a bias signal may be supplied to the lower electrode of the substrate support 11. Then, the scum S1 to S3 are removed by the plasma generated from the fourth process gas.

[0099] In step ST44, the fourth process gas may include at least one gas selected from the group consisting of a helium-containing gas, a hydrogen-containing gas, a bromine-containing gas, and a chlorine-containing gas. For example, the fourth process gas may include at least one gas selected from the group consisting of helium gas, hydrogen gas, hydrogen bromide gas, and boron trichloride gas. The fourth process gas may further include a noble gas such as Ar gas or an inert gas such as N2 gas.

[0100] In step ST44, a portion of the deposited film DF may be removed together with the scum S1 to S3. For example, a portion of the deposited film DF formed on the upper surface TS1 of the first region RM1 may also be removed. The deposited film DF may be removed in both the thickness direction and the width direction. In step ST44, a portion or all of the remainder of the second region RM2 may be removed together with the scum S1 to S3. That is, step ST44 and step ST45, which will be described later, may be performed simultaneously.

[0101] (Process ST45)

[0102] Next, in step ST45, the second region RM2 is further removed. In step ST45, the second region RM2 may be removed by plasma generated from a fifth process gas. For example, first, a fifth process gas is supplied from the gas supply unit 20 into the plasma processing space 10s. Next, a source RF signal is supplied to the upper electrode or the lower electrode. This generates a high-frequency electric field in the plasma processing space 10s, and plasma is generated from the fifth process gas. At this time, a bias signal may be supplied to the lower electrode of the substrate support 11. Then, the second region RM2 is removed by radicals contained in the plasma generated from the fifth process gas.

[0103] Note that a step of heating the substrate W may be performed after step ST42 and before step ST45. In this case, steps ST43 and ST44 may be omitted. The temperature of the substrate W in the step of heating the substrate W may be 180°C or higher or 190°C or higher. The temperature of the substrate W in the step of heating the substrate W may be 240°C or higher or 220°C or lower. Furthermore, the step of heating the substrate W and step ST45 may be performed using a single chamber, or may be performed using two or more different chambers. That is, the chamber used to perform the step of heating the substrate W and the chamber used in step ST45 may be the same chamber, i.e., a single chamber, or may be different chambers.

[0104] 13(b) is a diagram showing an example of the cross-sectional structure of the substrate W after processing in step ST45. As shown in FIG. 13(b), the second region RM2 is removed in step ST45. In step ST45, the deposited film DF formed on the second region RM2 may be entirely removed. Then, an opening OP defined by the side surface SS1 of the first region RM1 is formed in the base film UF. The upper surface of the base film UF is exposed in the opening OP.

[0105] In step ST45, the parameters of the plasma treatment for removing the second region RM2 can be set appropriately depending on the dimension (CD: Critical Dimension) of the first region RM1, which can be the target dimension after execution of step ST14.

[0106] In step ST45, the fifth process gas may be at least one selected from the gases listed as the first process gases, and may be the same gas as the first process gas. The fifth process gas may be at least one selected from the gases listed as the fourth process gases, and may be the same gas as the fourth process gas. Step ST45 can also be performed by the heat treatment apparatus 100 without generating plasma. In this case, the fifth process gas is supplied into the process chamber 102, the pressure in the process chamber is controlled to a predetermined pressure, and the temperature of the substrate W or the substrate support 121 is adjusted to a predetermined temperature.

[0107] In the method MT4, after a portion of the second region RM2 is removed in step ST42, steps ST43, ST44, and ST45 may be performed simultaneously. That is, after step ST42 is performed, a third process gas, a fourth process gas, and a fifth process gas are supplied from the gas supply unit 20 into the plasma processing space 10s. Next, a source RF signal is supplied to the upper electrode or the lower electrode. This generates a high-frequency electric field in the plasma processing space 10s, and plasma is generated from the third process gas, the fourth process gas, and the fifth process gas. At this time, a bias signal may be supplied to the lower electrode of the substrate support unit 11. Then, a deposited film DF is formed in the first region RM1 from radicals generated from the third process gas. Meanwhile, scum S1-S3 and the second region RM2 are removed by radicals generated from the fourth process gas and the fifth process gas. That is, the second region RM2 can be removed while protecting the first region RM1 with the deposited film DF. This allows the second region RM2 to be removed while appropriately controlling the size of the first region RM1.

[0108] Furthermore, in method MT4, after removing the second region RM2 in step ST42 and exposing at least a portion of the base film UF, steps ST43, ST44 and ST45 may be performed in this order, or steps ST43, ST44 and ST45 may be performed simultaneously.

[0109] According to method MT4, after removing at least a portion of second region RM2, the first region can be appropriately protected by the deposited film DF when removing the remainder of second region RM2 or the residue of the second region. Furthermore, in method MT4, the deposited film DF is formed on first region RM1, and then the remainder of second region RM2 or the residue of the second region is removed, so that surface roughness due to unevenness, etc., on the side surface SS1 of first region RM1 and the side surface of the deposited film DF can be reduced.

[0110] [Fifth embodiment]

[0111] The heat treatment system may include a heat treatment apparatus 100a shown in FIGS. 14(a) and 14(b) instead of the heat treatment apparatus 100 shown in FIG. 1. FIG. 14(a) is a schematic cross-sectional view illustrating an example of the configuration of the heat treatment apparatus 100a, and FIG. 14(b) is a schematic plan view illustrating an example of the configuration of the heat treatment apparatus 100a. The heat treatment apparatus 100a includes a shower head 141a and multiple gas nozzles 141b on a sidewall. The shower head 141a is provided on the ceiling of the processing chamber 102. The shower head 141a may be disposed to face the substrate support 121. The multiple gas nozzles 141b are provided on the sidewall of the processing chamber 102. The multiple gas nozzles 141b may be arranged, for example, at equal intervals along the circumferential direction on the sidewall of the processing chamber 102. The multiple gas nozzles 141b may include a first gas nozzle 141b1 and a second gas nozzle 141b2. The first gas nozzles 141b1 and the second gas nozzles 141b2 may be arranged alternately in the circumferential direction. The types of gases supplied into the processing chamber 102 from the shower head 141a, the first gas nozzle 141b1, and the second gas nozzle 141b2 may be the same or different. The flow rates of the gases supplied into the processing chamber 102 from the shower head 141a, the first gas nozzle 141b1, and the second gas nozzle 141b2 may be the same or different. Heaters (not shown) may be disposed on the sidewalls of the substrate support 121 and the processing chamber 102, similar to those of the heat treatment apparatus 100. A gas exhaust port (not shown) may be disposed on the bottom side of the processing chamber 102.

[0112] According to the thermal processing apparatus 100a, the gas density in the processing chamber 102 can be easily controlled, and the in-plane uniformity in the development of the resist film RM can be improved.

[0113] [Sixth embodiment]

[0114] As the substrate support, a substrate support 121a shown in FIG. 15 may be used instead of the substrate support 121 shown in FIG. 1. The substrate support 121a shown in FIG. 15 has multiple zones, each of which is provided with a heater electrode. The multiple zones are arranged along a plane orthogonal to the central axis of the substrate support 121a or a plane parallel to the substrate W. In the example shown in FIG. 15, the substrate support 121a has zones Z1 to Z14, each of which is provided with a heater electrode. The heater electrodes in each zone are configured so that power can be supplied independently. In other words, the substrate support 121a is configured so that the temperature can be controlled independently for each zone. Such a substrate support 121a can improve the in-plane uniformity in the development of the resist film RM.

[0115] [Seventh embodiment]

[0116] In the substrate processing method of the present disclosure, a precoat may be formed on the sidewalls and / or internal parts of the processing chamber 102, such as the substrate support 121, before starting substrate processing (development). The precoat may be formed by atomic layer deposition (ALD), chemical vapor deposition (CVD), or the like. A gas capable of forming a film resistant to a process gas containing carboxylic acid may be selected as the gas for forming the precoat. For example, a silicon-containing gas such as aminosilane or SiCl4 may be used. In this case, a silicon oxide film may be formed as the precoat on the sidewalls and / or internal parts of the processing chamber 102. This can suppress corrosion of the sidewalls and / or the substrate support 121 of the processing chamber 102 by the process gas.

[0117] Instead of or in addition to the pre-coating, the sidewalls and / or parts inside the processing chamber 102 may be made of a material that is resistant to processing gases containing carboxylic acids or the like.

[0118] In addition, in the substrate processing method of the present disclosure, the processing chamber 102 may be cleaned after the substrate processing (development). In this case, the processing chamber 102 and its internal components are heated, and then a cleaning gas is supplied into the processing chamber 102. Examples of the cleaning gas include a gas containing a hydrogen halide, such as HBr or HF. Cleaning may be performed by thermal atomic layer etching (hereinafter also referred to as "thermal ALE"). This allows metal oxides adhering to the sidewalls of the processing chamber 102 and / or the internal components during development to be removed.

[0119] [Eighth embodiment]

[0120] In the substrate processing method according to the eighth embodiment, the base film UF is etched using a resist film RM developed by any one of methods MT1 to MT4 as a mask. The etching conditions for the base film UF may be selected based on the film type of the base film UF. In one embodiment, the etching of the base film UF is performed by a plasma processing apparatus 1 shown in FIG.

[0121] <Configuration example of substrate processing system>

[0122] 16 is a block diagram illustrating an example of the configuration of a substrate processing system SS according to an exemplary embodiment. The substrate processing system SS includes a first carrier station CS1, a first processing station PS1, a first interface station IS1, an exposure apparatus EX, a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a controller CT.

[0123] The first carrier station CS1 loads and unloads the first carrier C1 between the first carrier station CS1 and a system external to the substrate processing system SS. The first carrier station CS1 has a mounting table with a plurality of first mounting plates ST1. The first carrier C1, which may contain a plurality of substrates W or be empty, is mounted on each first mounting plate ST1. The first carrier C1 has a housing capable of housing a plurality of substrates W therein. The first carrier C1 is, for example, a front-opening unified pod (FOUP).

[0124] The first carrier station CS1 also transports the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further includes a first transport device HD1. The first transport device HD1 is provided in the first carrier station CS1 so as to be located between the mounting table and the first processing station PS1. The first transport device HD1 transports and hands over the substrate W between the first carrier C1 on each first mounting plate ST1 and the second transport device HD2 of the first processing station PS1. The substrate processing system SS may further include a load lock module. The load lock module may be provided between the first carrier station CS1 and the first processing station PS1. The internal pressure of the load lock module can be switched between atmospheric pressure and vacuum. "Atmospheric pressure" may refer to the pressure inside the first transfer device HD1. "Vacuum" refers to a pressure lower than atmospheric pressure, and may be a medium vacuum of, for example, 0.1 Pa to 100 Pa. The inside of the second transport device HD2 may be atmospheric pressure or vacuum. The load lock module may, for example, transfer a substrate W from the first transport device HD1, which is at atmospheric pressure, to the second transport device HD2, which is at vacuum, and transfer a substrate W from the second transport device HD2, which is at vacuum, to the first transport device HD1, which is at atmospheric pressure.

[0125] The first processing station PS1 performs various processes on the substrate W. In one embodiment, the first processing station PS1 includes a pre-processing module PM1, a resist film forming module PM2, and a first thermal processing module PM3 (hereinafter collectively referred to as "first substrate processing modules PMa"). The first processing station PS1 also includes a second transfer device HD2 that transfers the substrate W. The second transfer device HD2 transfers and passes 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.

[0126] In the pre-treatment module PM1, the substrate W is subjected to pre-treatment. In one embodiment, the pre-treatment module PM1 includes a temperature adjustment unit that adjusts the temperature of the substrate W, a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision, etc. In one embodiment, the pre-treatment module PM1 includes a surface modification treatment unit that performs a surface modification treatment on the substrate W. Each treatment unit in the pre-treatment module PM1 may be configured to include a heat treatment device 100 (see FIG. 1), a plasma treatment device 1 (see FIGS. 2 and 3), and / or a liquid treatment device.

[0127] In the resist film formation module PM2, a resist film is formed on the substrate W. In one embodiment, the resist film formation module PM2 includes a dry coating unit. The dry coating unit forms a resist film on the substrate W using a dry process such as a vapor phase deposition method. In one example, the dry coating unit includes a CVD apparatus or an ALD apparatus that performs chemical vapor deposition of a resist film on the substrate W arranged in a chamber, or a PVD apparatus that performs physical vapor deposition of a resist film. The dry coating unit may be a thermal processing apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0128] In one embodiment, the resist film formation module PM2 includes a wet coating unit that forms a resist film on the substrate W using a wet process such as a solution coating method. The wet coating unit may be, for example, a liquid processing apparatus.

[0129] In one embodiment, an example of the resist film formation module PM2 includes both a wet coating unit and a dry coating unit.

[0130] In the first thermal treatment module PM3, the substrate W is subjected to a thermal treatment. In one embodiment, the first thermal treatment module PM3 includes one or more of a pre-bake (PAB) unit that performs a heat treatment on the substrate W on which a resist film has been formed, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0131] The first interface station IS1 has a third transfer device HD3. The third transfer device HD3 transfers and delivers substrates W between the first processing station PS1 and the exposure apparatus EX. The third transfer device HD3 has a housing that houses the substrates W, and may be configured so that the temperature, humidity, pressure, etc. within the housing are controllable.

[0132] The exposure apparatus EX uses an exposure mask (reticle) to expose a resist film on the substrate W. The exposure apparatus EX may be, for example, an EUV exposure apparatus having a light source that generates EUV light.

[0133] The second interface station IS2 has a fourth transport device HD4. The fourth transport device HD4 transports and delivers substrates W between the exposure apparatus EX and the second processing station PS2. The fourth transport device HD4 has a housing that houses the substrates W, and may be configured so that the temperature, humidity, pressure, etc. within the housing are controllable.

[0134] The second processing station PS2 performs various processes on the substrate W. In one embodiment, the second processing station PS2 includes a second thermal processing module PM4, a measurement module PM5, a development module PM6, and a third thermal processing module PM7 (hereinafter collectively referred to as "second substrate processing modules PMb"). The second processing station PS2 also includes a fifth transfer device HD5 that transfers the substrate W. The fifth transfer device HD5 transfers and passes 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.

[0135] The substrate W is subjected to a thermal treatment in the second thermal treatment module PM4. In one embodiment, the second thermal treatment module PM4 includes one or more of a post-exposure bake (PEB) unit that heat-treats the exposed substrate W, 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.

[0136] In the measurement module PM5, various measurements are performed on the substrate W. In one embodiment, the measurement module PM5 includes an imaging unit including a mounting stage for mounting the substrate W, an imaging device, an illumination device, and various sensors (temperature sensor, reflectance measurement sensor, etc.). The imaging device may be, for example, a CCD camera that captures an image of the appearance of the substrate W. Alternatively, the imaging device may be a hyperspectral camera that captures images by dispersing light into wavelengths. The hyperspectral camera can measure one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film.

[0137] In the developing module PM6, the substrate W is subjected to a development 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 FIGS. 2 and 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. In one embodiment, the developing module PM6 includes both a dry developing unit and a wet developing unit.

[0138] The substrate W is subjected to a thermal treatment in the third thermal treatment module PM7. In one embodiment, the third thermal treatment module PM7 includes one or more of a post-bake (PB) unit that heat-treats the developed substrate W, 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.

[0139] The second carrier station CS2 transfers the second carrier C2 between the second carrier station CS2 and a system external to the substrate processing system SS. The configuration and functions of the second carrier station CS2 may be similar to those of the first carrier station CS1 described above.

[0140] The control unit CT controls each component of the substrate processing system SS to perform a given process on the substrate W. The control unit CT stores a recipe in which the process procedure, process conditions, transport conditions, etc. are set, and controls each component of the substrate processing system SS to perform the given process on the substrate W in accordance with the recipe. The control unit CT may also have some or all of the functions of each control unit (the control unit 200 and control unit 2 shown in FIGS. 1 to 3, and the control unit of the liquid processing apparatus).

[0141] <Example of substrate processing method>

[0142] 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 step ST100 of pre-treating a substrate, step ST200 of forming a resist film on the substrate, step ST300 of performing a heat treatment (pre-bake: PAB) on the substrate on which the resist film has been formed, step ST400 of exposing the substrate to EUV light, step ST500 of performing a heat treatment (post-exposure bake: PEB) on the exposed substrate, step ST600 of measuring the substrate, step ST700 of developing the resist film on the substrate, step ST800 of performing a heat treatment (post-bake: PB) on the developed substrate, and 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 performed after step ST500.

[0143] The method MT may be performed using a substrate processing system SS shown in Fig. 16. In the following, an example will be described in which a control unit CT of the substrate processing system SS controls each part of the substrate processing system SS to perform the method MT on a substrate W.

[0144] (Process ST100: Pretreatment)

[0145] First, a first carrier C1 containing a plurality of substrates W is loaded into a first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on a first mounting plate ST1. Next, the first transport device HD1 sequentially removes each substrate W from the first carrier C1 and transfers them to a second transport device HD2 of the first processing station PS1. The substrates W are then transported by the second transport device HD2 to a pre-processing module PM1. The pre-processing module PM1 performs pre-processing on the substrates W. The pre-processing may include, for example, one or more of temperature adjustment of the substrates W, forming a part or all of an undercoat film on the substrates W, heating the substrates W, and high-precision temperature adjustment of the substrates W. The pre-processing may also include a surface modification process for the substrates W.

[0146] (Step ST200: Resist film formation)

[0147] 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 resist film is formed by a wet process such as a liquid phase deposition method. For example, a resist film is formed by spin-coating a resist film on the substrate W using a wet coating unit of the resist film formation module PM2. In one embodiment, the resist film is formed on the substrate W by a dry process such as a vapor phase deposition method. For example, a resist film is formed by vapor-depositing a resist film on the substrate W using a dry coating unit of the resist film formation module PM2.

[0148] The resist film may be formed on the substrate W using both a dry process and a wet process. For example, after a first resist film is formed on the substrate W by a dry process, a second resist film may be formed on the first resist film by a wet process. In this case, the film thickness, material, and / or composition of the first resist film and the second resist film may be the same or different.

[0149] (Process ST300:PAB)

[0150] Next, the substrate W is transported by the second transport device HD2 to the first thermal treatment module PM3. The first thermal treatment module PM3 subjects the substrate W to a heat treatment (pre-baking: PAB). The pre-baking may be performed in an air atmosphere or an inert atmosphere. The pre-baking may be performed by heating the substrate W to a temperature of 50°C or higher and 250°C or lower, 50°C or higher and 200°C or lower, or 80°C or higher and 150°C or lower. When a resist film is formed by a dry process in step ST200, in one embodiment, the pre-baking may be performed in the dry coating unit that performed step ST200. In one embodiment, after the pre-baking, a process (Edge Bead Removal: EBR) may be performed to remove the resist film from the edge of the substrate W.

[0151] (Step ST400: EUV exposure)

[0152] Next, the substrate W is transferred by the second transfer device HD2 to the third transfer device HD3 of the first interface station IS1. The substrate W is then transferred by the third transfer device HD3 to the exposure device EX. The substrate W is subjected to EUV exposure via an exposure mask (reticle) in the exposure device EX. As a result, a first region that has been EUV exposed and a second region that has not been EUV exposed are formed on the substrate W, corresponding to the pattern of the exposure mask (reticle).

[0153] (Process ST500:PEB)

[0154] Next, the substrate W is transferred from the fourth transfer device HD4 of the second interface station IS2 to the fifth transfer device HD5 of the second processing station PS2. The substrate W is then transferred by the fifth transfer device HD5 to the second thermal treatment module PM4. The substrate W is then subjected to a heat treatment (post-exposure bake: PEB) in the second thermal treatment module PM4. The post-exposure bake may be performed in an air atmosphere. The post-exposure bake may also be performed by heating the substrate W to a temperature of 180°C or higher and 250°C or lower.

[0155] (Process ST600: Measurement)

[0156] Next, the substrate W is transported to the measurement module PM5 by the fifth transport device HD5. The measurement module PM5 measures the substrate W. The measurement may be 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 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.

[0157] In one embodiment, the control unit CT determines whether or not there is an exposure abnormality in the substrate W based on the measured appearance, dimensions, and / or pattern shape of the substrate W. In one embodiment, if the control unit CT determines that there is an exposure abnormality, the substrate W may be reworked or discarded without being developed in step ST700. Reworking of the substrate W may be performed by removing the resist on the substrate W and returning to step ST200 to form a resist film again. Reworking after development may cause damage to the substrate W, but by performing rework before development, damage to the substrate W can be avoided or suppressed.

[0158] (Process ST700: Development)

[0159] Next, the substrate W is transferred to the developing module PM6 by the fifth transfer device HD5. In the developing module PM6, the resist film on the substrate W is developed. The developing process may be performed by dry development or wet development. The developing process may be performed by a combination of dry development and wet development. The developing process in step ST700 may be performed by a first method (see FIGS. 5 and 11) or a second method (see FIGS. 12(a) and 12(b)). After or during the developing process, a desorption process may be performed one or more times. The desorption process includes descumming or smoothing the surface of the resist film using an inert gas such as helium or a plasma of the inert gas. Furthermore, in the developing module PM6, after the developing process, a portion of the base film may be etched using the developed resist film as a mask.

[0160] (Process ST800:PB)

[0161] Next, the substrate W is transferred by the fifth transfer device HD5 to the third thermal treatment module PM7, where it is subjected to a heat treatment (post-bake). The post-bake may be performed in an air atmosphere or a reduced-pressure atmosphere containing N2 or O2. 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 thermal treatment module PM4 instead of the third thermal treatment module PM7. In one embodiment, after the post-bake, the measurement module PM5 may perform optical measurement of the substrate W. This measurement may be performed in addition to or instead of the measurement in step ST600. In one embodiment, the controller CT determines whether or not there are any abnormalities, such as defects, scratches, or foreign matter, in the developed pattern of the substrate W, based on the measured appearance, dimensions, and / or pattern shape of the substrate W. In one embodiment, if the controller CT determines that there is an abnormality, the substrate W may be reworked or discarded without being etched in step ST900. In one embodiment, if it is determined that there is an abnormality in the control unit CT, the opening dimensions of the resist film on the substrate W may be adjusted using a dry coating unit (CVD apparatus, ALD apparatus, etc.).

[0162] (Process ST900: Etching)

[0163] After step ST800 is performed, the substrate W is transferred by the fifth transfer device HD5 to the sixth transfer device HD6 of the second carrier station CS2, and then transferred by the sixth transfer device HD6 to the second carrier C2 of the second mounting plate ST2. The second carrier C2 is then transferred to a plasma processing system (not shown). In the plasma processing system, the undercoat film UF of the substrate W is etched using the developed resist film as a mask. This completes the method MT. When the resist film is developed using a plasma processing device in step ST700, etching may be performed subsequently in a plasma processing chamber of the plasma processing device. Furthermore, when the second processing station PS2 includes a plasma processing module in addition to the developing module PM6, etching may be performed in the plasma processing module. The above-described desorption process may be performed one or more times before or during etching.

[0164] Although various exemplary embodiments have been described above, the present invention is not limited to the above-described exemplary embodiments, and various additions, omissions, substitutions, and modifications may be made. Furthermore, elements in different embodiments may be combined to form other embodiments.

[0165] Various experiments are described below, along with their results. In the following description, reference is made to Figures 18(a) and 18(b), 19(a) to 19(d), 20 to 22, 23(a) to 23(c), 24(a) and 24(b), 25, and 26. These figures show the results of various experiments. In these figures, "Unexposed" indicates the results of an experiment in which development was performed on an unexposed resist film, and "Exposed" indicates the results of an experiment in which development was performed on a resist film exposed to EUV light. In these figures, "Thickness" indicates the thickness of the resist film, and "Normalized Thickness" indicates the thickness of the resist film normalized by the thickness of the resist film before development. The resist film contained tin oxide. The experiments shown in these figures used the thermal processing system shown in Figure 1. The relationship between development time and resist film thickness was also determined in the experiments shown in these figures.

[0166] (Experiment 1)

[0167] In Experiment 1, unexposed and exposed resist films were developed using a process gas consisting of a mixture of HBr and Ar gases. In Experiment 1, the partial pressure of the HBr gas was set to 0.2 Torr (26.6 Pa). In Experiment 1, the temperature of the substrate support during development was set to 10°C or 20°C.

[0168] Figure 18(a) shows the results of an experiment where the temperature of the substrate support during development was 10°C, and Figure 18(b) shows the results of an experiment where the temperature of the substrate support during development was 60°C. When the temperature of the substrate support was 10°C and HBr gas was used during development, it was confirmed that unexposed resist film residues tended to be generated, as shown in Figure 18(a). Furthermore, when the temperature of the substrate support was 60°C and HBr gas was used during development, it was confirmed that the unexposed resist film could be removed, but the difference between the rate of thickness reduction of the unexposed resist film and the rate of thickness reduction of the exposed resist film could be reduced, as shown in Figure 18(b). That is, when HBr gas was used, it was confirmed that setting the temperature of the substrate support during development at a high temperature could remove the unexposed regions of the resist film, but the selectivity during development could be reduced.

[0169] (Experiment 2)

[0170] In Experiment 2, unexposed and exposed resist films were developed using a process gas containing only carboxylic acid. In Experiment 2, the carboxylic acid pressure, i.e., the process gas pressure, was set to 5 Torr (666 Pa). In Experiment 2, the temperature of the substrate support during development was set to 120°C. In Experiment 2, formic acid (H-COOH), trifluoroacetic acid (CF3-COOH), or acetic acid (CH3-COOH) was used as the carboxylic acid.

[0171] Figures 19(b), 19(c), and 19(d) show the results when formic acid, trifluoroacetic acid, and acetic acid were used as the carboxylic acid, respectively. Figure 19(a) shows the same results as Figure 18(b). As shown in these figures, when a carboxylic acid is used in development, it was confirmed that it is possible to suppress the reduction in the thickness of the exposed resist film and obtain a high selectivity, even when the temperature of the substrate support is high. It was also confirmed that a particularly high development rate was obtained when formic acid or trifluoroacetic acid was used.

[0172] (Experiment 3)

[0173] In Experiment 3, unexposed and exposed resist films were developed using a process gas containing only formic acid (H-COOH). In Experiment 3, the pressure of the formic acid, i.e., the process gas pressure, was set to 0.5 Torr (66.6 Pa) or 5 Torr (666 Pa). In Experiment 3, the temperature of the substrate support during development was set to 60°C, 120°C, or 180°C.

[0174] Figure 20 shows the results of Experiment 3. When formic acid was used, it was confirmed that development with a high selectivity was possible at temperatures of 120°C or higher, as shown in Figure 20. It was also confirmed that when formic acid was used with the substrate support temperature at 180°C, the reduction in the thickness of the exposed resist film was more suppressed than when formic acid was used with the substrate support temperature at 120°C.

[0175] (Experiment 4)

[0176] In Experiment 4, unexposed and exposed resist films were developed using a process gas containing only trifluoroacetic acid (CF3-COOH). In Experiment 4, the pressure of the trifluoroacetic acid, i.e., the process gas pressure, was set to 0.5 Torr (66.6 Pa) or 5 Torr (666 Pa). In Experiment 4, the temperature of the substrate support during development was set to 60°C, 120°C, or 180°C.

[0177] FIG. 21 shows the results of Experiment 4. When trifluoroacetic acid was used, it was confirmed that development with a high selectivity was possible at temperatures of 120°C or higher, as shown in FIG. 21. Furthermore, it was confirmed that when trifluoroacetic acid was used with the substrate support temperature at 180°C, the reduction in thickness of the exposed resist film was more suppressed than when trifluoroacetic acid was used with the substrate support temperature at 120°C. Furthermore, it was confirmed that when trifluoroacetic acid was used, the reduction in thickness of the exposed resist film was more suppressed than when formic acid was used.

[0178] (Experiment 5)

[0179] In Experiment 5, unexposed and exposed resist films were developed using a process gas containing only acetic acid (CH3-COOH). In Experiment 5, the pressure of the acetic acid, i.e., the process gas pressure, was set to 0.5 Torr (66.6 Pa) or 5 Torr (666 Pa). In Experiment 5, the temperature of the substrate support during development was set to 120°C or 180°C.

[0180] Figure 22 shows the results of Experiment 5. When acetic acid was used, it was confirmed that development with a high selectivity was possible at temperatures of 120°C or higher, as shown in Figure 22. Furthermore, it was confirmed that when acetic acid was used, the reduction in thickness of the exposed resist film was more suppressed than when formic acid or trifluoroacetic acid was used, but the rate of reduction in thickness of the unexposed resist film was relatively slow.

[0181] (Experiment 6)

[0182] In Experiment 6, a mixture of trifluoroacetic acid (CF3-COOH) and Ar gas was used as the process gas to develop both the unexposed and exposed resist films. In Experiment 6, the partial pressure of trifluoroacetic acid was set to 3 Torr (400 Pa). In Experiment 6, the temperature of the substrate support during development was set to 90°C, 120°C, or 180°C.

[0183] Figures 23(a), 23(b), and 23(c) show the results when the temperature of the substrate support during development was 90°C, 120°C, and 180°C, respectively. As shown in these figures, it was confirmed that when trifluoroacetic acid was used, development that selectively removed the unexposed areas was possible when the substrate support temperature during development was 90°C or higher.

[0184] (Experiment 7)

[0185] In Experiment 7, a mixture of trifluoroacetic acid (CF3-COOH) and Ar gas was used as the process gas to develop both the unexposed and exposed resist films. In Experiment 7, the temperature of the substrate support during development was set to 120°C. In Experiment 7, the partial pressure of trifluoroacetic acid was set to 0.36 (48 Pa), 0.6 Torr (80 Pa), 3 Torr (400 Pa), or 6 Torr (798 Pa).

[0186] Figure 24(a) shows the results for developing an unexposed resist film, and Figure 24(b) shows the results for developing an exposed resist film. As shown in these figures, when trifluoroacetic acid is used, it was confirmed that development that selectively removes the unexposed region is possible by setting the trifluoroacetic acid partial pressure to 0.36 Torr or higher. Furthermore, when trifluoroacetic acid is used, it was confirmed that development with a high selectivity is possible by setting the trifluoroacetic acid partial pressure to 0.6 Torr or higher.

[0187] (Experiment 8)

[0188] In Experiment 8, a mixture of acetic acid (CH3-COOH) and Ar gas was used as the process gas to develop both the unexposed and exposed resist films. In Experiment 8, the temperature of the substrate support during development was set to 120°C, 150°C, 180°C, or 210°C. In Experiment 8, the partial pressure of acetic acid was set to 0.6 Torr (80 Pa), 3 Torr (400 Pa), or 6 Torr (800 Pa).

[0189] Figure 25 shows the results of Experiment 8. As shown in Figure 25, when acetic acid was used, it was confirmed that development that selectively removed the unexposed regions was possible by setting the partial pressure of acetic acid to 0.6 Torr or higher. It was also confirmed that when acetic acid was used, development that selectively removed the unexposed regions was possible by setting the temperature of the substrate support to 120°C or higher. It was also confirmed that when acetic acid was used, unexposed regions could be removed quickly, i.e., a high development rate could be obtained, by setting the temperature of the substrate support to 180°C or higher.

[0190] (Experiment 9)

[0191] In Experiment 9, unexposed and exposed resist films were developed using a process gas consisting of a mixture of acetic acid (CH3-COOH) and Ar gas. In Experiment 9, the temperature of the substrate support during development was set to 120°C or 150°C. In Experiment 9, the partial pressure of acetic acid was set to 6 Torr (800 Pa), 12 Torr (1600 Pa), 21 Torr (2800 Pa), 30 Torr (4000 Pa), or 60 Torr (8000 Pa).

[0192] Figure 26 shows the results of Experiment 9. As shown in Figure 26, when acetic acid was used, it was confirmed that development that selectively removed the unexposed regions was possible by setting the partial pressure of acetic acid in the range of 6 Torr to 60 Torr. It was also confirmed that when acetic acid was used, development that selectively removed the unexposed regions was possible by setting the temperature of the substrate support to a temperature of 120°C or higher. It was also confirmed that when acetic acid was used, the higher the temperature of the substrate support, given the same partial pressure of acetic acid, the faster the unexposed regions could be removed, i.e., a higher development rate could be obtained.

[0193] Various exemplary embodiments included in the present disclosure are now described in [E1] to [E19] below.

[0194] [E1] (a) providing a substrate on a substrate support in a processing chamber, the substrate having an undercoat film and a resist film formed from a metal-containing resist disposed on the undercoat film, the resist film having a first region and a second region; (b) supplying a process gas containing a carboxylic acid into the process chamber and exposing the substrate to the carboxylic acid to selectively remove the second region relative to the first region, thereby dry developing the resist film; Including, In the method (b), the pressure or partial pressure of the carboxylic acid is 40 Pa or more and less than 13,332 Pa.

[0195] [E2] The substrate processing method according to E1, wherein in (b), the pressure or partial pressure of the carboxylic acid is 133 Pa or more.

[0196] [E3] The substrate processing method according to E1, wherein in (b), the pressure or partial pressure of the carboxylic acid is 666 Pa or more.

[0197] [E4] The substrate processing method according to E1, wherein in (b), the pressure or partial pressure of the carboxylic acid is 1333 Pa or less.

[0198] [E5] The substrate processing method according to E1, wherein the processing gas contains an inert gas, and in (b), the partial pressure of the carboxylic acid is 40 Pa or more.

[0199] [E6] The substrate processing method according to E5, wherein the partial pressure of the carboxylic acid is 8000 Pa or less.

[0200] [E7] The substrate processing method according to any one of E1 to E6, wherein in (b), the temperature of the substrate support part is 90° C. or higher.

[0201] [E8] The substrate processing method according to any one of E1 to E6, wherein in (b), the temperature of the substrate support part is 120° C. or higher.

[0202] [E9] The substrate processing method according to any one of E1 to E6, wherein in (b), the temperature of the substrate support part is 300° C. or less.

[0203] [E10] The substrate processing method according to E1, wherein the carboxylic acid is at least one selected from the group consisting of formic acid, trifluoroacetic acid, and acetic acid.

[0204] [E11] the carboxylic acid is formic acid; In the method (b), the temperature of the substrate support is 120° C. or higher, and the pressure or partial pressure of the carboxylic acid is 40 Pa or higher. The substrate processing method according to E8.

[0205] [E12] the carboxylic acid is trifluoroacetic acid; In the method (b), the temperature of the substrate support is 90° C. or higher, and the pressure or partial pressure of the carboxylic acid is 40 Pa or higher. The substrate processing method according to E8.

[0206] [E13] the carboxylic acid is acetic acid; In the method (b), the temperature of the substrate support is 120° C. or higher, and the pressure or partial pressure of the carboxylic acid is 40 Pa or higher. The substrate processing method according to E8.

[0207] [E14] The above (b) is (b-1) performing dry development on the resist film under first conditions; (b-2) performing dry development on the resist film under second conditions different from the first conditions; Including, a combination of the first condition and the second condition satisfies one or more of conditions (A), (B), and (C); The condition (A) includes developing the resist using a first process gas in the (b-1) and developing the resist film using a second process gas different from the first process gas in the (b-2), wherein at least one of the first process gas and the second process gas contains the carboxylic acid, The condition (B) includes developing the resist film by setting a pressure of the carboxylic acid to a first pressure in the (b-1) step, and developing the resist film by setting a pressure of the carboxylic acid to a second pressure different from the first pressure in the (b-2) step; The condition (C) includes setting the substrate supporting part to a first temperature in the (b-1) to develop the resist film, and setting the substrate supporting part to a second temperature different from the first temperature in the (b-2) to develop the resist film. The substrate processing method according to any one of E1 to E13.

[0208] [E15] the period during which (b) is performed includes a first period and a second period alternating with the first period; a combination of the processing conditions for the first period and the processing conditions for the second period satisfies one or more of conditions (A), (B), and (C); The condition (A) includes developing the resist film using a first process gas during the first period, and developing the resist film using a second process gas different from the first process gas during the second period, wherein at least one of the first process gas and the second process gas contains the carboxylic acid, the condition (B) includes developing the resist film by setting a pressure of the carboxylic acid to a first pressure during the first period, and developing the resist film by setting a pressure of the carboxylic acid to a second pressure different from the first pressure during the second period; the condition (C) includes developing the resist film by setting the temperature of the substrate supporting part to a first temperature during the first period, and developing the resist film by setting the temperature of the substrate supporting part to a second temperature different from the first temperature during the second period; The substrate processing method according to any one of E1 to E13.

[0209] [E16] In (b), the second region is partially removed; The substrate processing method includes: After (b), forming a deposition film on the first region; removing residues generated in step (b) while protecting the first region with the deposited film; removing the remainder of the second region; The substrate processing method according to any one of E1 to E13, further comprising:

[0210] [E17] the deposited film is a carbon-containing film or a silicon-containing film, The residue is removed by plasma of a treatment gas containing at least one gas selected from the group consisting of a helium-containing gas, a hydrogen-containing gas, a bromine-containing gas, and a chlorine-containing gas. A method for processing a substrate according to E16.

[0211] [E18] In (b), the second region is partially removed; The substrate processing method includes: After (b), heating the substrate; removing the remainder of the second region; The substrate processing method according to any one of E1 to E13, further comprising:

[0212] In the embodiment of E18, the temperature of the substrate in the step of heating the substrate may be 180°C or higher or 190°C or higher. In the embodiment of E18, the temperature of the substrate in the step of heating the substrate may be 240°C or higher or 220°C or lower. In the embodiment of E18, the step of heating the substrate and the step of removing the residue may be performed using a single chamber, or may be performed using two or more different chambers. That is, the chamber used for performing the step of heating the substrate and the chamber used for the step of removing the residue may be the same chamber, i.e., a single chamber, or may be different chambers.

[0213] [E19] a processing chamber; a substrate support disposed within the processing chamber; a gas supply configured to supply a process gas comprising a carboxylic acid into the chamber; an exhaust mechanism connected to the processing chamber; A control unit; Equipped with the control unit is configured to control the gas supply unit and the exhaust mechanism to supply the process gas into the chamber and adjust the pressure or partial pressure of the carboxylic acid to 40 Pa or more and less than 13,332 Pa for dry development of a resist film on a substrate placed on the substrate support unit. Substrate processing system.

[0214] From the foregoing, it will be understood that various embodiments of the present disclosure have been described herein for purposes of illustration, and that various modifications may be made without departing from the scope and spirit of the present disclosure. Accordingly, the various embodiments disclosed herein are not intended to be limiting, with the true scope and spirit being indicated by the appended claims. [Explanation of symbols]

[0215] 1...plasma processing apparatus, 2...control unit, 10...plasma processing chamber, 11...substrate support unit, 20...gas supply unit, 30...power supply, 100...heat processing apparatus, 102...processing chamber, 120...stage heater, 121...substrate support unit, 141...gas nozzle, 200...control unit, OP...opening, RM...resist film, RM1...first region, RM2...second region, UF...base film, W...substrate.

Claims

1. An apparatus for dry developing a tin-containing resist, Processing chamber and Within the processing chamber, a substrate support portion is configured to support the substrate containing the tin-containing resist, A gas supply unit configured to supply a processing gas containing at least one carboxylic acid selected from the group consisting of formic acid, acetic acid, and trifluoroacetic acid into the processing chamber, An exhaust mechanism configured to exhaust the processing gas from the processing chamber, The control unit is configured to control the partial pressure of carboxylic acid in the processed gas using the gas supply unit and the exhaust mechanism, A device equipped with the following features.

2. The apparatus according to claim 1, wherein the control unit is configured to control the partial pressure of the carboxylic acid to 40 Pa or more using the gas supply unit and the exhaust mechanism.

3. The apparatus according to claim 1 or 2, wherein the control unit is configured to control the partial pressure of the carboxylic acid to less than 13,332 Pa using the gas supply unit and the exhaust mechanism.

4. The gas supply unit includes at least one flow controller, The apparatus according to claim 1, wherein the at least one flow controller is configured to control the flow rate of the carboxylic acid supplied into the processing chamber.

5. The apparatus according to claim 1, wherein the gas supply unit includes at least one gas source.

6. The apparatus according to claim 1, wherein the gas supply unit includes a vaporizer configured to vaporize a liquid material.

7. Further comprising at least one heater selected from the group consisting of a stage heater in the substrate support portion, a ceiling heater in the ceiling wall constituting the processing chamber, and a side wall heater in the side wall constituting the processing chamber, The apparatus according to claim 1, wherein the control unit is configured to control the temperature of the substrate supported by the substrate support portion to 90°C or higher using the at least one heater.

8. The apparatus according to claim 1, wherein the substrate support portion includes a ring assembly arranged to surround the substrate.

9. The apparatus according to claim 8, wherein the ring assembly includes a plurality of annular members.

10. The apparatus according to claim 8 or 9, wherein the ring assembly is made of an inorganic material or an organic material.

11. An apparatus for dry developing a tin-containing resist, Processing chamber and Within the processing chamber, a substrate support portion is configured to support the substrate containing the tin-containing resist, A gas supply unit configured to supply a processing gas containing a carboxylic acid into the processing chamber, An exhaust mechanism configured to exhaust the processing gas from the processing chamber, The control unit is configured to control the partial pressure of carboxylic acid in the processed gas using the gas supply unit and the exhaust mechanism, A device equipped with the following features.

12. The apparatus according to claim 11, wherein the carboxylic acid includes a halogen element.

13. The apparatus according to claim 11, wherein the carboxylic acid comprises at least one selected from the group consisting of monofluoroacetic acid, difluoroacetic acid, and trifluoroacetic acid.

14. The apparatus according to claim 11, wherein the carboxylic acid comprises at least one selected from the group consisting of monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid.

15. The apparatus according to claim 11, wherein the carboxylic acid comprises at least one selected from the group consisting of formic acid, acetic acid, and trifluoroacetic acid.

16. The apparatus according to claim 11, wherein the processing gas further comprises at least one selected from the group consisting of an inert gas, an inorganic acid gas, an organic acid gas other than the carboxylic acid, and an oxidizing gas.

17. (a) A step of providing a substrate containing a tin-containing resist in a processing chamber, wherein the tin-containing resist has a first region and a second region, (b) A step of selectively removing the second region from the first region, Includes, The above (b) is, (b1) A step of supplying a processing gas containing at least one carboxylic acid selected from the group consisting of formic acid, acetic acid, and trifluoroacetic acid into the processing chamber, (b2) A step of exhausting the processing gas from the processing chamber, (b3) A step of controlling the partial pressure of the carboxylic acid in the processing gas, A dry development method, including the following.

18. The dry developing method according to claim 17, wherein in (b3), the partial pressure of the carboxylic acid is controlled to 40 Pa or more.

19. The dry developing method according to claim 17 or 18, wherein in (b3), the partial pressure of the carboxylic acid is controlled to be less than 13332 Pa.

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