Substrate Processing Method and Substrate Processing System

Abstract

Provided is a method for processing a substrate. The method for processing a substrate includes (a) a step in which a substrate is provided on a substrate support in a processing chamber, the substrate having a base film and a resist film formed from a metal-containing resist and provided on the base film, wherein the metal-containing resist has a first region and a second region. The method for processing a substrate further includes (b) a step in which a processing gas containing carboxylic acid is supplied into a processing chamber, the substrate is exposed to the carboxylic acid, and the second region is selectively removed with respect to the first region, and thus dry developing is performed on the resist film. In (b), the pressure or partial pressure of the carboxylic acid is 0.3 Torr (40 Pa) to 100 Torr (13,332 Pa) (exclusive of 100 Torr).

Description

Cross - reference to related applications

[0001] This application claims the priority of U.S. Provisional Patent Application No. 63 / 393,377, entitled "SUBSTRATE TREATMENT METHOD AND SUBSTRATE TREATMENT SYSTEM", filed on July 29, 2022, and incorporates the entire disclosure of the U.S. Provisional Patent Application herein by reference.

Technical Field

[0002] Exemplary embodiments of the present disclosure relate to a substrate treatment method and a substrate treatment system.

Background Art

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

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present disclosure provides a technique for appropriately performing dry development on an exposed metal - containing resist.

Means for Solving the Problems

[0006] In one exemplary embodiment of the present disclosure, a substrate processing method is provided. The substrate processing method includes (a) providing a substrate having an underlayer film and a resist film formed from a metal-containing resist provided on the underlayer film on a substrate support in a processing chamber, the metal-containing resist having a first region and a second region. The substrate processing method further includes (b) supplying a processing gas containing a 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 to perform dry development on the resist film. In (b), the pressure or partial pressure of the carboxylic acid is 0.3 Torr (40 Pa) or more and less than 100 Torr (13332 Pa).

Advantages 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 Description of the Drawings

[0008]

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Embodiments for Carrying Out the Invention

[0009] A substrate processing method according to one exemplary embodiment of the present disclosure includes: (a) providing a substrate having an underlayer film and a resist film formed from a metal-containing resist provided on the underlayer film on a substrate support in a processing chamber, the metal-containing resist having a first region and a second region. The substrate processing method further includes: (b) supplying a processing gas containing a 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 to perform dry development on the resist film. In (b), the pressure or partial pressure of the carboxylic acid is 0.3 Torr (40 Pa) or more and less than 100 Torr (13332 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 denoted by the same reference numerals, and redundant descriptions are omitted. Unless otherwise specified, the positional relationships such as up, down, left, and right are described based on the positional relationships shown in the drawings. The dimensional ratios in the drawings do not represent actual ratios, and the actual ratios are not limited to the ratios shown in the drawings.

[0011] <Configuration Example of Heat Treatment System>

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

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

[0014] A substrate support portion 121 is provided on the lower side inside the processing chamber 102. The substrate support portion 121 constitutes a placement portion on which a substrate W is placed. The substrate support portion 121 is, for example, circular in plan view, and the substrate W is placed on its horizontally formed surface (upper surface). A stage heater 120 is embedded in the substrate support portion 121. This stage heater 120 can heat the substrate W placed on the substrate support portion 121. Note that a ring assembly (not shown) may be arranged around the substrate W on the substrate support portion 121. The ring assembly may include one or a plurality of annular members. By arranging the ring assembly around the substrate W, the temperature controllability of the outer peripheral region of the substrate W can be improved. The ring assembly may be composed of an inorganic material or an organic material according to the intended heat treatment.

[0015] The substrate support portion 121 is supported inside the processing chamber 102 by columns 122 provided on the bottom surface of the processing chamber 102. A plurality of lift pins 123 that can move vertically are provided on the outer side in the circumferential direction of the columns 122. Each of the plurality of lift pins 123 is inserted into a through hole provided in the substrate support portion 121. The plurality of lift pins 123 are arranged at intervals in the circumferential direction. The lifting and lowering operations of the plurality of lift pins 123 are brought about by a lifting mechanism 124. When the lift pins 123 project from the surface of the substrate support portion 121, it becomes possible to transfer the substrate W between a transfer mechanism (not shown) and the substrate support portion 121.

[0016] On the side wall of the processing chamber 102, an exhaust port 131 having an opening is provided. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump, a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. By adjusting the exhaust flow rate and the like by this exhaust mechanism 132, the pressure inside the processing chamber 102 is adjusted. Note that on the side wall of the processing chamber 102, a transfer port for the substrate W (not shown) is formed to be openable and closable at a position different from the position where the exhaust port 131 opens.

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

[0018] The gas nozzle 141 is formed in a rod shape protruding from the side wall of the processing chamber 102 toward the center side of the processing chamber 102. The tip of the gas nozzle 141 extends horizontally from the side wall of the processing chamber 102, for example. 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. Note that 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] Note that the gas nozzle 141 may be provided on the ceiling wall of the processing chamber 102, for example. Also, the exhaust port 131 may be provided on the bottom surface of the processing chamber 102.

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

[0021] The control unit 200 processes computer-executable instructions for causing the heat treatment apparatus 100 to execute various processes described in the present disclosure. The control unit 200 may be configured to control each element of the heat treatment apparatus 100 to execute the various processes described herein. In one embodiment, part or all of the control unit 200 may be included in the heat treatment apparatus 100. The control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3. The control unit 200 is realized by, for example, a computer 200a. The processing unit 200a1 may be configured to read a program from the storage unit 200a2 and perform various control operations by executing the read program. This program may be stored in the storage unit 200a2 in advance, or may be acquired via a medium when necessary. The acquired program is stored in the storage unit 200a2 and read from the storage unit 200a2 by the processing unit 200a1 and executed. The medium may be various storage media readable by the computer 200a, or may be a communication line connected to the communication interface 200a3. The processing unit 200a1 may be a CPU (Central Processing Unit). The storage unit 200a2 may include a RAM (Random Access Memory), a ROM (Read Only Memory), an HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 may communicate with the heat treatment apparatus 100 via a communication line such as a LAN (Local Area Network).

[0022] <Configuration Example of Plasma Processing System>

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

[0024] The plasma generation unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be capacitively coupled plasma (CCP), inductively coupled plasma (ICP), ECR plasma (Electron-Cyclotron-resonance plasma), helicon wave plasma (HWP), surface wave plasma (SWP), or the like. Also, various types of plasma generation units including an AC (Alternating Current) plasma generation unit and a DC (Direct Current) plasma generation unit may be used. In one embodiment, the AC signal (AC power) used in the AC plasma generation unit has a frequency within the range of 100 kHz to 10 GHz. Accordingly, the AC signal includes an RF (Radio Frequency) signal and a microwave signal. In one embodiment, the RF signal has a frequency within 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 execute various processes described in the present disclosure. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to execute the various processes described herein. In one embodiment, part or all of the control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 is realized by, for example, a computer 2a. The control unit 2 may include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. Each configuration of the control unit 2 may be the same as each configuration of the control unit 200 (see FIG. 1) described above.

[0026] Hereinafter, a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1 will be described. FIG. 3 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0027] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power source 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support unit 11 and a gas introduction unit. The gas introduction unit is configured to introduce at least one processing gas into the plasma processing chamber 10. The gas introduction unit includes a shower head 13. The substrate support unit 11 is disposed in the plasma processing chamber 10. The shower head 13 is disposed above the substrate support unit 11. In one embodiment, the shower head 13 constitutes at least a part of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the shower head 13, the side wall 10a of the plasma processing chamber 10, and the substrate support unit 11. The plasma processing chamber 10 is grounded. The shower head 13 and the substrate support unit 11 are electrically insulated from the housing of the plasma processing chamber 10.

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

[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 other members surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member, may have the annular region 111b. In this case, the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating member, or may be disposed on both the electrostatic chuck 1111 and the annular insulating member. Also, at least one RF / DC electrode coupled to the RF power supply 31 and / or the DC power supply 32 described later may be disposed within the ceramic member 1111a. In this case, at least one RF / DC electrode functions as a lower electrode. When the bias RF signal and / or the DC signal described later is supplied to at least one RF / DC electrode, the RF / DC electrode is also referred to as a bias electrode. Note that the conductive member of the base 1110 and at least one RF / DC electrode may function as a plurality of lower electrodes. Also, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support portion 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 ring is formed of a conductive material or an insulating material, and the cover ring is formed of an insulating material.

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

[0032] The shower head 13 is configured to introduce at least one process gas from the gas supply unit 20 into the plasma processing space 10s. The shower head 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and a plurality of gas introduction ports 13c. The process gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the plurality of gas introduction ports 13c. Further, the shower head 13 includes at least one upper electrode. The gas introduction portion may include, in addition to the shower head 13, one or more side gas injection portions (SGI) attached to one or more openings formed in the side wall 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 the corresponding gas source 21 to the shower head 13 via the corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Further, the gas supply unit 20 may include at least one flow modulation device for modulating or pulsing the flow rate of 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. Thereby, plasma is formed from at least one process gas supplied to the plasma processing space 10s. Accordingly, the RF power supply 31 can function as at least a part of the plasma generation unit 12. Also, by supplying a bias RF signal to at least one lower electrode, a bias potential is generated on the substrate W, and the ion component in the formed plasma can be drawn into the substrate W.

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

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

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

[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 pulse waveform that is rectangular, trapezoidal, triangular, or a combination thereof. In one embodiment, a waveform generation unit for generating a sequence of voltage pulses from a DC signal is connected between the first DC generation unit 32a and at least one lower electrode. Accordingly, the first DC generation unit 32a and the waveform generation unit constitute a voltage pulse generation unit. When the second DC generation unit 32b and the waveform generation unit constitute a voltage pulse generation unit, the voltage pulse generation unit is connected to at least one upper electrode. The voltage pulses may have a positive polarity or a negative polarity. Also, the sequence of voltage pulses may include one or more positive-polarity voltage pulses and one or more negative-polarity voltage pulses within one period. Note that the first and second DC generation units 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generation unit 32a may be provided in place of the second RF generation unit 31b.

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

[0040] <Substrate Processing Method>

[0041] Hereinafter, various embodiments of the substrate processing method in the present disclosure will be described.

[0042] [First Embodiment]

[0043] FIG. 4 is a flowchart showing a substrate processing method (hereinafter also referred to as "method MT1") according to the first embodiment. 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 (hereinafter also referred to as "dry development") using a processing gas.

[0044] Method MT1 may be executed using any one of the above-described substrate processing systems (see FIGS. 1 to 3), or may be executed using two or more of these substrate processing systems. For example, method MT1 may be executed in a heat treatment system (see FIG. 1). Hereinafter, method MT1 will be described by taking as an example the case where the control unit 200 controls each part of the heat treatment apparatus 100 to apply method MT1 to the substrate W.

[0045] (Step ST11: Provision of Substrate)

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

[0047] FIG. 5 is a diagram showing an example of a cross-sectional structure of the substrate W provided in step ST11 of the substrate processing method shown in FIG. 4. The substrate W includes an underlayer film UF and a resist film RM formed on the underlayer film UF. The substrate W may be used in the manufacture of semiconductor devices. Semiconductor devices include, for example, memory devices such as DRAM and 3D-NAND flash memories and logic devices.

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

[0049] As shown in FIG. 5, the resist film RM has an exposed first region RM1 and an unexposed second region RM2. The first region RM1 is a region exposed to EUV light, that is, an EUV exposure region. The second region RM2 is a region not exposed to EUV light, that is, an unexposed region.

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

[0051] FIGS. 6 and 7 are diagrams each showing an example of the underlayer film UF of the substrate W. As shown in FIG. 6, the underlayer 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 underlayer film UF may be composed of the second film UF2 and the third film UF3.

[0052] The first film UF1 is, for example, a spin-on glass (SOG) film, a SiC film, a SiON film, a silicon-containing antireflection film (SiARC), or an organic film. The second film UF2 is, for example, a spin-on carbon (SOC) film, an amorphous carbon film, or a silicon-containing film. The third film UF3 is, for example, a silicon-containing film. The silicon-containing film is, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbonitride film, a polycrystalline silicon film, or a carbon-containing silicon film. The third film UF3 may be composed of a plurality of 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. Also, the third film UF3 may be composed of alternately stacked silicon oxide films and polycrystalline silicon films. Also, the third film UF3 may be a stacked film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. Also, the third film UF3 may be composed of stacked silicon oxide films and silicon carbonitride films. Also, the third film UF3 may be a stacked 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 photoresist film containing a metal is formed on an underlayer film that has been subjected to an adhesion improvement treatment or the like. The film formation may be performed by a dry process, may also be performed by a wet process such as a solution coating method, or may be performed by both a dry process and a wet process. Note that, before forming the photoresist film, a surface modification treatment of the underlayer film may be performed. The substrate after forming the photoresist film undergoes a heat treatment, that is, post apply bake (PAB). An additional heat treatment may be performed on the substrate after PAB. The substrate after the heat treatment is transported to an exposure apparatus, and the photoresist film is irradiated with EUV light through an exposure mask (reticle). Thereby, a substrate W including an underlayer film UF and a resist film RM having an exposed first region RM1 and an unexposed second region RM2 is formed. The first region RM1 is a region corresponding to an opening provided in the exposure mask (reticle). The second region RM2 is a region corresponding to a pattern provided in the exposure mask (reticle). The EUV light has a wavelength in the range of, for example, 10 to 20 nm. The EUV light may have a wavelength in the range of 11 to 14 nm, and in one example, has a wavelength of 13.5 nm. The substrate W after exposure is transported from the exposure apparatus to a heat treatment apparatus under atmosphere control and undergoes a heat treatment, that is, post exposure bake (PEB). An additional heat treatment may be performed on the substrate W after PEB.

[0054] (Step ST12: Development of Substrate)

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

[0056] In process ST12, the processing gas is supplied into the processing chamber 102 through the gas nozzle 141. In one embodiment, the processing gas contains a carboxylic acid. In one embodiment, the carboxylic acid may be formic acid (HCOOH). In one embodiment, the carboxylic acid may be acetic acid (CH3COOH). In one embodiment, the carboxylic acid may contain 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 (CFH2COOH), difluoroacetic acid (CF2HCOOH), and trifluoroacetic acid (CF3COOH), and may be trifluoroacetic acid. The carboxylic acid containing chlorine may be, for example, at least one selected from the group consisting of monochloroacetic acid (CClH2COOH), dichloroacetic acid (CCl2HCOOH), and trichloroacetic acid (CCl3COOH). 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, and may be trifluoroacetic acid.

[0057] The processing gas may further contain an inert gas. The inert gas may be nitrogen gas or a noble gas such as Ar. Further, the processing gas may further contain an inorganic acid or an organic acid other than the carboxylic acid in addition to the inert gas. Further, the processing gas may contain an oxidizing gas such as O2 gas and / or CO2 gas.

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

[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) or more, 5 Torr (666 Pa) or more. Also, 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, 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 can be achieved 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 (selection ratio) can be achieved together with a high development rate.

[0060] Also, in step ST12, the temperature of the substrate W or the substrate support portion 121 can be controlled. In one embodiment, the temperature of the substrate support portion 121 in step ST12 may be -20°C or higher, may be 0°C or higher, may be 20°C or higher, may be 90°C or higher, may be 120°C or higher. Also, the temperature of the substrate support portion 121 in step ST12 may be 300°C or lower, may be 220°C or lower, may be 210°C or lower, may be 200°C or lower. In one embodiment, the temperature of the substrate support portion 121 is controlled to be -20°C or higher and 220°C or lower. If the temperature of the substrate support portion 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 portion 121 is less than 200°C, a high development contrast (selection ratio) can be achieved together with a high development rate. The temperature of the substrate support portion 121 can be controlled by the power supplied to the stage heater 120. Also, the temperature of the substrate support portion 121 may be controlled by the power supplied to the side wall heater 104 and / or the ceiling heater 130 together with or instead of the stage heater 120. Also, the temperature of the substrate support portion 121 may be controlled by an infrared lamp, microwaves, etc. together with or instead of the power supplied to the above-described heaters.

[0061] In step ST12, when the carboxylic acid in the processing gas is formic acid, the temperature of the substrate support portion 121 may be 120°C or higher. In step ST12, when the carboxylic acid in the processing 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 processing gas is trifluoroacetic acid, the temperature of the substrate support portion 121 may be 90°C or higher, and may be 120°C or higher. In step ST12, when the carboxylic acid in the processing 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 processing gas is acetic acid, the temperature of the substrate support portion 121 may be 120°C or higher, may be 150°C or higher, and may be 180°C or higher. In step ST12, when the carboxylic acid in the processing 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 underlying 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 surrounded by the side surface on the underlying film UF. The opening OP has a shape corresponding to the second region RM2 (resulting in a shape corresponding to the exposure mask pattern used for EUV exposure) in a plan view of the substrate W. The shape may be, for example, a circle, an ellipse, a rectangle, a line, or a shape combining one or more of these. The developed resist film RM may be provided with a plurality of openings OP. The plurality of openings OP may each have a linear shape and may be arranged at regular intervals to form a line-and-space pattern. Also, the plurality of openings OP may be arranged in a grid pattern to form a pillar pattern.

[0063] According to the first embodiment, the second region RM2 can be removed with a high selection ratio with respect to the first region RM1 (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"). Further, according to the first embodiment, the generation of residues due to development can be suppressed.

[0064] Subsequently, a substrate processing method according to another embodiment of the present disclosure will be described. In the following, parts overlapping with the first embodiment will be described briefly or omitted.

[0065] [Second Embodiment]

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

[0067] In one embodiment, the combination of the first condition and the second condition may satisfy any one or more of the following conditions (A) to (C), and may satisfy any two or more of them. In the following description as well, the pressure of the carboxylic acid is the pressure of the carboxylic acid when the processing gas is a single gas, and is 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 processing gas, and in step ST22-2, the resist film RM is developed using a second processing gas different from the first processing gas. (B) In step ST22-1, the resist film RM is developed by setting the pressure of the carboxylic acid to a first pressure, and in step ST22-2, the resist film RM is developed by setting the pressure of the carboxylic acid to a second pressure different from the first pressure. (C) In step ST22-1, the substrate support portion 121 is set to a first temperature to develop the resist film RM, and in step ST22-2, the substrate support portion 121 is set to a second temperature different from the first temperature to develop the resist film RM.

[0069] In an example satisfying condition (A), a gas containing an inorganic acid may be used as the first processing gas, and a gas containing a carboxylic acid may be used as the second processing gas. The inorganic acid may be a gas with a higher acidity 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 any one or more of the above-described carboxylic acids.

[0070] In another example satisfying condition (A), a gas containing an organic acid other than a carboxylic acid may be used as the first processing gas, and a gas containing a carboxylic acid may be used as the second processing gas. Alternatively, a gas containing a carboxylic acid may be used as the first processing gas, and a gas containing an organic acid other than a carboxylic acid may be used as the second processing gas. Alternatively, a gas containing a carboxylic acid may be used as the first processing gas, and a gas containing a carboxylic acid or an organic acid other than a carboxylic acid having an acidity lower than that of the first processing gas may be used as the second processing gas. The organic acid other than a carboxylic acid may be a β-dicarbonyl compound such as acetylacetone (CH3C(O)CH2C(O)CH3), trichloroacetylacetone (CCl3C(O)CH2C(O)CH3), hexachloroacetylacetone (CCl3C(O)CH2C(O)CCl3), trifluoroacetylacetone (CF3C(O)CH2C(O)CH3), hexafluoroacetylacetone (HFAc, CF3C(O)CH2C(O)CF3), etc., or an alcohol such as nonafluoro-tert-butyl alcohol ((CF3)3C-OH). The carboxylic acid may be any one or more of the above-described carboxylic acids.

[0071] In yet another example that satisfies condition (A), a gas containing a first carboxylic acid may be used as the first processing gas, and a gas containing a second carboxylic acid different from the first carboxylic acid may be used as the second processing gas. The acidity of the second carboxylic acid may be lower than that 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, or 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 contains a carboxylic acid and an inert gas. In this case, in step ST22-1, the partial pressure of the carboxylic acid may be set to a first pressure, and in step ST22-2, the partial pressure of the carboxylic acid may be set to a second pressure different from the first pressure. 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 processing gas contains a carboxylic acid and an inorganic acid such as HBr. In this case, in step ST22-1, the partial pressure of the carboxylic acid may be set to a first pressure, and in step ST22-2, the partial pressure of the carboxylic acid may be set to a second pressure different from the first pressure. The second pressure may be higher than the first pressure. In one example, the first pressure may be 30 Torr or more and 50 Torr or less, and the second pressure may be 80 Torr or more and 90 Torr or less.

[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 more and 130°C or less, and the second temperature may be 70°C or more and 90°C or less.

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

[0076] [Third Embodiment]

[0077] Each of FIGS. 10(a), 10(b), and 10(c) is a timing chart showing an example of a substrate processing method (hereinafter also referred to as "method MT3") according to the third embodiment. Method MT3 includes step ST31 and step ST32. In step ST31, the substrate W is provided in the same manner as in step ST11 of 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 a second period alternating with the first period.

[0078] In one embodiment, the combination of the processing conditions in the first period and the processing conditions in the second period may satisfy any one or more of the following conditions (A) to (C), and may satisfy any two or more of them. Note that also in the following description, the pressure of the carboxylic acid is the pressure of the carboxylic acid when the processing gas is a single gas, and is the partial pressure of the carboxylic acid when the processing gas is a mixed gas.

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

[0080] In an example satisfying condition (A), a gas containing an inorganic acid may be used as the first processing gas, and a gas containing a carboxylic acid may be used as the second processing 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 any one or more of the carboxylic acids described above.

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

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

[0083] In an example satisfying condition (B), the first pressure may be 0 Torr or more and 0.1 Torr or less, and the second pressure may be 1 Torr or more and 10 Torr or less.

[0084] In an example satisfying condition (C), the first temperature may be 110°C or more and 130°C or less, and the second temperature may be 170°C or more and 190°C or less.

[0085] According to method MT3, the developing step (ST32) includes a first period and a second period alternating with the first period. Therefore, the volatilization of the reaction by-products generated in step ST32 is promoted, and the generation of residues in step ST32 can be suppressed. In the timing charts shown in FIGS. 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, but they may also be controlled to be "High" in the first period and "Low" in the second period.

[0086] [Fourth Embodiment]

[0087] FIG. 11 is a flowchart showing a substrate processing method (hereinafter also referred to as "method MT4") according to the fourth embodiment. 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 deposited 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 developing processing system. In method MT4, the heat treatment apparatus 100 as shown in FIG. 1 can also be used. In this case, the processing chamber 102 can 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. Hereinafter, the case where the plasma processing system shown in FIG. 3 is used as the developing processing system will be taken as an example to describe method MT4.

[0089] (Steps ST41 to ST42)

[0090] In step ST41, a substrate W is provided in the same manner as in step ST11. In the subsequent step ST42, a part of the second region RM2 is removed by developing the resist film RM. In step ST42, the development may be stopped before the underlying film UF is exposed. A part of the second region RM2 may be removed by the same process as the process of step ST12 described above. The processing gas used in step ST42 is the same processing gas as the processing gas used in step ST11. Each of FIGS. 12(a) and 12(b) is a diagram showing 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 that cannot be completely removed by the process of step ST42 are generated. The scum S1 to S3 can be removed in a subsequent step ST44 (descum process).

[0091] (Step 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 can be formed by plasma generated from a third processing gas containing a carbon-containing gas or a silicon-containing gas. In one example, first, the third processing 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. Thereby, a high-frequency electric field is generated in the plasma processing space 10s, and plasma is generated from the third processing gas. Then, radicals containing carbon or silicon contained in the plasma can be deposited on at least a part of the resist film RM.

[0093] Fig. 13(a) is a diagram showing an example of the cross-sectional structure of the substrate W after step ST43. As shown in Fig. 13(a), 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" is also 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 can be formed thicker on the upper surface TS1 than on the side surface SS1 of the first region RM1. Further, the deposited film DF may be further 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 is wide. Also, the deposited film DF can 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 forming a carbon-containing film as the deposited film DF, the third processing gas may include a gas containing carbon and hydrogen. The gas may be, for example, a hydrocarbon (C x H y : x and y are positive integers. Also referred to as a CH-based gas). In one example, it may be CH4 gas, C2H2 gas, C2H4 gas, or C3H6 gas. The gas may be a fluorocarbon (CxFz: x and z are positive integers. Also referred to as a CF-based gas). In one example, it may be C4F6 or C4F8. Further, the gas may be a hydrofluorocarbon (C x H y F z : x, y, and z are positive integers. Also referred to as a CHF-based gas). In one example, it may be CH2F2 gas or CH3F gas.

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

[0096] In one embodiment, after forming a silicon-containing film as the deposition film DF, a carbon-containing film may be formed. In this case, the process ST44 described below may be executed simultaneously with the formation of the carbon-containing film. In one embodiment, after forming a carbon-containing film as the deposition film DF, a silicon-containing film may be formed. In this case, the process ST44 described below may be executed simultaneously with the formation of the silicon-containing film. Note that in the process ST43, a bias signal (a bias RF signal or a pulsed first DC signal) may not be supplied to the lower electrode of the substrate support portion 11.

[0097] (Process ST44)

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

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

[0100] Note that in step ST44, a part of the deposited film DF may be removed together with the scums S1 to S3. For example, a part of the deposited film DF formed on the upper surface TS1 of the first region RM1 may also be removed. The deposited film DF can be removed in both its thickness direction and width direction. Also, in step ST44, a part or all of the remainder of the second region RM2 may be removed together with the scums S1 to S3. That is, step ST44 and step ST45 described later may be executed simultaneously.

[0101] (Step 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 the fifth processing gas. In one example, first, the fifth processing 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. Thereby, a high-frequency electric field is generated in the plasma processing space 10s, and plasma is generated from the fifth processing gas. At this time, a bias signal may be supplied to the lower electrode of the substrate support unit 11. Then, the second region RM2 is removed by radicals contained in the plasma generated from the fifth processing gas.

[0103] Note that, after step ST42 and before step ST45, a step of heating the substrate W may be performed. 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 lower or 220°C or lower. Also, 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, that is, a single chamber, or may be different chambers from each other.

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

[0105] In process ST45, the parameters of the plasma process for removing the second region RM2 can be appropriately set according to the dimension (CD: Critical Dimension) of the first region RM1. The dimension can be the target dimension after the execution of process ST14.

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

[0107] In method MT4, after a part of the second region RM2 is removed in process ST42, processes ST43, ST44, and ST45 may be executed simultaneously. That is, after the execution of process ST42, the third processing gas, the fourth processing gas, and the fifth processing gas are supplied into the plasma processing space 10s from the gas supply unit 20. Next, a source RF signal is supplied to the upper electrode or the lower electrode. Thereby, a high-frequency electric field is generated in the plasma processing space 10s, and plasma is generated from the third processing gas, the fourth processing gas, and the fifth processing gas. At this time, a bias signal may be supplied to the lower electrode of the substrate support portion 11. Then, a deposited film DF is formed on the first region RM1 from the radicals generated from the third processing gas. On the other hand, the scum S1 to 3 and the second region RM2 are removed by the radicals generated from the fourth processing gas and the fifth processing gas. That is, the second region RM2 can be removed while protecting the first region RM1 by the deposited film DF. Thereby, the second region RM2 can be removed while appropriately controlling the dimension of the first region RM1.

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

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

[0110] [Fifth Embodiment]

[0111] Instead of the heat treatment apparatus 100 shown in FIG. 1, the heat treatment system may include a heat treatment apparatus 100a shown in FIGS. 14(a) and 14(b). FIG. 14(a) is a schematic cross-sectional view showing a configuration example of the heat treatment apparatus 100a, and FIG. 14(b) is a schematic plan view showing a configuration example of the heat treatment apparatus 100a. The heat treatment apparatus 100a includes a shower head 141a and a plurality of gas nozzles 141b on the side wall. The shower head 141a is provided on the ceiling of the processing chamber 102. The shower head 141a may be arranged to face the substrate support portion 121. The plurality of gas nozzles 141b are provided on the side wall of the processing chamber 102. The plurality of gas nozzles 141b may be arranged at equal intervals along the circumferential direction on the side wall of the processing chamber 102, for example. The plurality of gas nozzles 141b may include a first gas nozzle 141b1 and a second gas nozzle 141b2. The first gas nozzle 141b1 and the second gas nozzle 141b2 may be arranged alternately along the circumferential direction. The types of gas supplied into the processing chamber 102 from each of the shower head 141a, the first gas nozzle 141b1, and the second gas nozzle 141b2 may be the same or different. Also, the flow rates of the gas supplied into the processing chamber 102 from each of the shower head 141a, the first gas nozzle 141b1, and the second gas nozzle 141b2 may be the same or different. Note that heaters (not shown) may be arranged on each of the substrate support portion 121 and the side wall of the processing chamber 102 in the same manner as in the heat treatment apparatus 100. Also, a gas exhaust port (not shown) may be arranged on the bottom side of the processing chamber 102.

[0112] According to the heat treatment 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 portion, instead of the substrate support portion 121 shown in FIG. 1, the substrate support portion 121a shown in FIG. 15 may be used. The substrate support portion 121a shown in FIG. 15 has a plurality of zones, and each zone is provided with a heater electrode. The plurality of zones are arranged along a plane orthogonal to the central axis of the substrate support portion 121a or a plane parallel to the substrate W. In the example shown in FIG. 15, the substrate support portion 121a has zones Z1 to Z14, and each zone has a heater electrode. The heater electrodes of each zone are configured such that power can be supplied independently to each of them. That is, the substrate support portion 121a is configured to be temperature controllable independently for each zone. According to such a substrate support portion 121a, the in-plane uniformity in the development of the resist film RM can be improved.

[0115] [Seventh Embodiment]

[0116] In the substrate processing method of the present disclosure, before the start of substrate processing (development), a precoat may be performed on the side walls of the processing chamber 102 and / or parts in the processing chamber 102 such as the substrate support portion 121 (hereinafter also referred to as "parts in the chamber"). The precoat may be performed by an atomic layer deposition method (Atomic Layer Deposition: hereinafter also referred to as "ALD method"), a chemical vapor deposition method (Chemical Vapor Deposition: hereinafter also referred to as "CVD method"), or the like. As the gas for forming the precoat, a gas capable of forming a film having resistance to a processing gas containing carboxylic acid may be selected. In one example, a silicon-containing gas such as aminosilane or SiCl4 can be used. In this case, a silicon oxide film can be formed as the precoat on the side walls of the processing chamber 102 and / or the parts in the chamber. Thereby, corrosion of the side walls of the processing chamber 102 and / or the substrate support portion 121 and the like by the processing gas can be suppressed.

[0117] Note that instead of or together with the precoat, the side walls of the processing chamber 102 and / or the parts in the chamber may be made of a material having resistance to a processing gas containing carboxylic acid or the like.

[0118] Also, in the substrate processing method of the present disclosure, after substrate processing (development), the inside of the processing chamber 102 may be cleaned. In this case, after heating the processing chamber 102 and the parts inside the chamber, a cleaning gas is supplied into the processing chamber 102. As the cleaning gas, for example, a gas containing hydrogen halide such as HBr or HF can be used. The cleaning may be performed by a thermal atomic layer etching method (hereinafter also referred to as "thermal ALE method"). Thereby, the metal oxides attached to the side walls of the processing chamber 102 and / or the parts inside the chamber during development can be removed.

[0119] [Eighth Embodiment]

[0120] In the substrate processing method according to the eighth embodiment, the underlying film UF is etched using the resist film RM developed by any one of the methods MT1 to MT4 as a mask. The etching conditions for the underlying film UF may be selected based on the film type of the underlying film UF and the like. In one embodiment, the etching of the underlying film UF is performed by the plasma processing apparatus 1 shown in FIG. 3.

[0121] <Configuration Example of Substrate Processing System>

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

[0123] The first carrier station CS1 performs the loading and unloading of 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 having a plurality of first mounting plates ST1. On each first mounting plate ST1, the first carrier C1 in a state of accommodating a plurality of substrates W or in an empty state is placed. The first carrier C1 has a housing capable of accommodating a plurality of substrates W therein. In one example, the first carrier C1 is a FOUP (Front Opening Unified Pod).

[0124] Also, the first carrier station CS1 transports the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further includes a first transfer device HD1. The first transfer 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 transfer device HD1 transports and transfers the substrate W between the first carrier C1 on each first mounting plate ST1 and the second transfer device HD2 of the first processing station PS1. The substrate processing system SS may further include a load lock module. The load lock module may be provided between the first carrier station CS1 and the first processing station PS1. The load lock module can switch the pressure inside thereof between atmospheric pressure and vacuum. "Atmospheric pressure" can be the pressure inside the first transfer device HD1. "Vacuum" is a pressure lower than atmospheric pressure and can be, for example, a medium vacuum of 0.1 Pa to 100 Pa. The inside of the second transfer device HD2 can be atmospheric pressure or vacuum. The load lock module may, for example, transport the substrate W from the first transfer device HD1 at atmospheric pressure to the second transfer device HD2 at vacuum, and also transport the substrate W from the second transfer device HD2 at vacuum to the first transfer device HD1 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 pretreatment module PM1, a resist film forming module PM2, and a first heat treatment module PM3 (hereinafter also collectively referred to as the "first substrate processing module PMa"). Further, the first processing station PS1 has a second transfer device HD2 for transferring the substrate W. The second transfer device HD2 transfers and delivers the substrate W between two designated first substrate processing modules PMa, and between the first processing station PS1 and the first carrier station CS1 or the first interface station IS1.

[0126] In the pretreatment module PM1, pretreatment is performed on the substrate W. In one embodiment, the pretreatment module PM1 includes a temperature adjustment unit for adjusting the temperature of the substrate W, a high-precision temperature control unit for adjusting the temperature of the substrate W with high precision, and the like. In one embodiment, the pretreatment module PM1 includes a surface modification processing unit for performing surface modification processing on the substrate W. Each processing unit of the pretreatment module PM1 may be configured to include a heat treatment apparatus 100 (see FIG. 1), a plasma processing apparatus 1 (see FIGS. 2 and 3), and / or a liquid processing apparatus.

[0127] In the resist film forming module PM2, a resist film is formed on the substrate W. In one embodiment, the resist film forming module PM2 includes a dry coating unit. The dry coating unit forms a resist film on the substrate W using a dry process such as a vapor deposition method. The dry coating unit, for example, includes a CVD apparatus or an ALD apparatus for chemically vapor-depositing a resist film or a PVD apparatus for physically vapor-depositing a resist film on the substrate W disposed in the chamber. The dry coating unit may be a heat treatment apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0128] In one embodiment, the resist film forming module PM2 includes a wet coating unit. The wet coating unit forms a resist film on the substrate W using a wet process such as a 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 forming module PM2 includes both a wet coating unit and a dry coating unit.

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

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

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

[0133] The second interface station IS2 has a fourth transfer device HD4. The fourth transfer device HD4 transfers and delivers the substrate W between the exposure device EX and the second processing station PS2. The fourth transfer device HD4 may have a housing for accommodating the substrate W, and may be configured such that the temperature, humidity, pressure, etc. inside 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 heat treatment module PM4, a measurement module PM5, a development module PM6, and a third heat treatment module PM7 (hereinafter also collectively referred to as the "second substrate processing module PMb"). Further, the second processing station PS2 has a fifth transfer device HD5 for transferring the substrate W. The fifth transfer device HD5 transfers and delivers the substrate W between two designated second substrate processing modules PMb, and between the second processing station PS2 and the second carrier station CS2 or the second interface station IS2.

[0135] In the second heat treatment module PM4, heat treatment is performed on the substrate W. In one embodiment, the second heat treatment module PM4 includes any one or more of a post-exposure bake (PEB) unit for performing heat treatment on the exposed substrate W, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature control unit for precisely adjusting the temperature of the substrate W. Each of these units may have one or more heat treatment apparatuses. In one example, a plurality of heat treatment apparatuses may be stacked. The heat treatment apparatus may be, for example, the heat treatment apparatus 100 (see FIG. 1). Each heat treatment may be performed at a predetermined temperature using a predetermined gas.

[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 that includes a stage on which the substrate W is placed, an imaging device, an illumination device, and various sensors (such as a temperature sensor, a reflectance measurement sensor, etc.). The imaging device may be, for example, a CCD camera that images the appearance of the substrate W. Alternatively, the imaging device may be a hyperspectral camera that spectrally separates light for each wavelength and performs imaging. The hyperspectral camera can measure any one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film.

[0137] In the development module PM6, a development process is performed on the substrate W. In one embodiment, the development module PM6 includes a dry development unit that performs dry development on the substrate W. The dry development unit may be, for example, a heat treatment device 100 (see FIG. 1) or a plasma treatment device 1 (see FIGS. 2 and 3). In one embodiment, the development module PM6 includes a wet development unit that performs wet development on the substrate W. The wet development unit may be, for example, a liquid treatment device. In one embodiment, the development module PM6 includes both a dry development unit and a wet development unit.

[0138] In the third heat treatment module PM7, a heat treatment is performed on the substrate W. In one embodiment, the third heat treatment module PM7 includes any one or more of a post bake (PB) unit that performs a heat treatment on the developed substrate W, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature control unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment devices. In one example, the plurality of heat treatment devices may be stacked. The heat treatment device may be, for example, the heat treatment device 100 (see FIG. 1). Each heat 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 outside the substrate processing system SS. The configuration and function of the second carrier station CS2 may be similar to those of the first carrier station CS1 described above.

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

[0141] <An example of a 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, the method MT includes a step ST100 of performing a pre-treatment on a substrate, a step ST200 of forming a resist film on the substrate, a step ST300 of performing a heat treatment (pre-bake: PAB) on the substrate on which the resist film has been formed, a step ST400 of performing EUV exposure on the substrate, a step ST500 of performing a heat treatment (post-exposure bake: PEB) on the substrate after the exposure, a step ST600 of measuring the substrate, a step ST700 of developing the resist film on the substrate, a step ST800 of performing a heat treatment (post-bake: PB) on the substrate after the development, and a step ST900 of etching the substrate. The method MT may not include one or more of the above steps. For example, the method MT may not include the step ST600, and the step ST700 may be performed after the step ST500.

[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 controller CT of the substrate processing system SS controls each part of the substrate processing system SS to perform the method MT on a substrate W.

[0144] (Process ST100: Pretreatment)

[0145] First, a first carrier C1 containing a plurality of substrates W is carried into a first carrier station CS1 of a substrate processing system SS. The first carrier C1 is placed on a first mounting plate ST1. Next, by a first transfer device HD1, each substrate W in the first carrier C1 is sequentially taken out and delivered to a second transfer device HD2 of a first processing station PS1. The substrate W is transferred to a pretreatment module PM1 by the second transfer device HD2. The pretreatment module PM1 performs pretreatment on the substrate W. The pretreatment may include, for example, one or more of temperature adjustment of the substrate W, formation of part or all of an underlying film of the substrate W, heat treatment of the substrate W, and high-precision temperature adjustment of the substrate W. The pretreatment may include a surface modification treatment of the substrate W.

[0146] (Process ST200: Resist Film Formation)

[0147] Next, the substrate W is transferred to a resist film formation module PM2 by the second transfer device HD2. A resist film is formed on the substrate W by the resist film formation module PM2. In one embodiment, the formation of the resist film is performed by a wet process such as a liquid phase deposition method. For example, a resist film is formed by spin-coating a resist film on the substrate W using a wet coating unit of the resist film formation module PM2. In one embodiment, the formation of the resist film on the substrate W is performed by a dry process such as a vapor phase deposition method. For example, a resist film is formed by depositing a resist film on the substrate W using a dry coating unit of the resist film formation module PM2.

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

[0149] (Step ST300: PAB)

[0150] Next, the substrate W is transported to the first heat treatment module PM3 by the second transport device HD2. The first heat treatment module PM3 performs a heat treatment (pre-bake: PAB) on the substrate W. The pre-bake may be performed in an air atmosphere or an inert atmosphere. Further, the pre-bake may be performed by heating the substrate W to 50°C or higher, 250°C or lower, 50°C or higher, 200°C or lower, or 80°C or higher and 150°C or lower. When forming a resist film by a dry process in Step ST200, in one embodiment, the pre-bake may be continuously performed in the dry coating unit that executed Step ST200. In one embodiment, after the pre-bake, a process of removing the resist film at the edge of the substrate W (Edge Bead Removal: EBR) may be performed.

[0151] (Step ST400: EUV Exposure)

[0152] Next, the substrate W is transferred to the third transport device HD3 of the first interface station IS1 by the second transport device HD2. Then, the substrate W is transported to the exposure apparatus EX by the third transport device HD3. The substrate W is subjected to EUV exposure through an exposure mask (rectangle) in the exposure apparatus EX. As a result, on the substrate W, a first region subjected to EUV exposure and a second region not subjected to EUV exposure are formed corresponding to the pattern of the exposure mask (rectangle).

[0153] (Step 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. Then, the substrate W is transferred to the second heat treatment module PM4 by the fifth transfer device HD5. And, the substrate W is subjected to a heat treatment (post-exposure bake: PEB) in the second heat treatment module PM4. The post-exposure bake may be performed in an air atmosphere. Also, the post-exposure bake may be performed by heating the substrate W to 180°C or higher and 250°C or lower.

[0155] (Step ST600: Measurement)

[0156] Next, the substrate W is transferred to the measurement module PM5 by the fifth transfer device HD5. The measurement of the substrate W is performed by the measurement module PM5. The measurement may be an optical measurement or other measurement. In one embodiment, the measurement by the measurement module PM5 includes the 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 the measurement of any one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0157] In one embodiment, the control unit CT determines the presence or absence of exposure abnormality of the substrate W based on the measured appearance, dimensions, and / or pattern shape, etc. of the substrate W. In one embodiment, when it is determined that there is an exposure abnormality in the control unit CT, the substrate W may be reworked or discarded without performing development in step ST700. The rework of the substrate W may be performed by removing the resist on the substrate W and returning to step ST200 again to form a resist film. Rework after development may involve damage to the substrate W, but by performing rework before development, damage to the substrate W can be avoided or suppressed.

[0158] (Step ST700: Development)

[0159] Next, the substrate W is conveyed to the development module PM6 by the fifth conveyance device HD5. In the development module PM6, the resist film on the substrate W is developed. The development process may be performed by dry development or wet development. The development process may also be performed by combining dry development and wet development. The development process in step ST700 may be performed by the first method (see FIGS. 5 and 11) or the second method (see FIGS. 12(a) and 12(b)). After the development process or during the development process, the desorption process may be executed one or more times. The desorption process includes removing scum (descum) or smoothing the surface from the surface of the resist film by an inert gas such as helium or plasma of the inert gas. Also, in the development module PM6, after the development process, a part of the underlying film may be etched using the developed resist film as a mask.

[0160] (Step ST800: PB)

[0161] Next, the substrate W is transported to the third heat treatment module PM7 by the fifth transport device HD5 and subjected to heat treatment (post-bake). The post-bake may be performed in an air atmosphere or in a reduced-pressure atmosphere containing N2 or O2. Also, the post-bake may be performed by heating the substrate W to 150°C or higher and 250°C or lower. The post-bake may be performed in the second heat treatment module PM4 instead of the third heat treatment module PM7. In one embodiment, after the post-bake, optical measurement of the substrate W may be performed by the measurement module PM5. Such measurement may be performed in addition to or instead of the measurement in step ST600. In one embodiment, based on the measured appearance, dimensions, and / or pattern shape, etc. of the substrate W, the control unit CT determines the presence or absence of abnormalities such as defects, scratches, and foreign matter adhesion in the developed pattern of the substrate W. In one embodiment, when it is determined that there is an abnormality in the control unit CT, rework or discard of the substrate W may be performed without performing the etching in step ST900. In one embodiment, when it is determined that there is an abnormality in the control unit CT, the opening dimension of the resist film on the substrate W may be adjusted using a dry coating unit (CVD device, ALD device, etc.).

[0162] (Step ST900: Etching)

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

[0164] As described above, various exemplary embodiments have been described. However, the present invention is not limited to the above-described exemplary embodiments, and various additions, omissions, substitutions, and changes may be made. Also, it is possible to form other embodiments by combining elements in different embodiments.

[0165] The following describes various experiments along with their results. In the following description, reference is made to FIGS. 18(a) and 18(b), FIGS. 19(a) to 19(d), FIGS. 20 to 22, FIGS. 23(a) to 23(c), FIGS. 24(a) and 24(b), FIG. 25, and FIG. 26. These figures show the results of various experiments. In these figures, "Unexposed" shows the results of an experiment in which development was performed on an unexposed resist film, and "Exposed" shows the results of an experiment in which development was performed on an EUV-light-exposed resist film. Also, 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 in the state before development. Note that the resist film was a resist film containing tin oxide. Also, in the experiments whose results are shown in these figures, the heat treatment system shown in FIG. 1 was used. Also, in the experiments whose results are shown in these figures, the relationship between the development time (Time) and the thickness of the resist film was obtained.

[0166] (Experiment 1)

[0167] In Experiment 1, development was performed on each of an unexposed resist film and an exposed resist film using a processing gas that was a mixed gas of HBr gas and Ar gas. 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 portion during development was set to 10°C or 20°C.

[0168] Fig. 18(a) shows the results of an experiment when the temperature of the substrate support during development is 10°C, and Fig. 18(b) shows the results of an experiment when the temperature of the substrate support during development is 60°C. In development, when the temperature of the substrate support is 10°C and HBr gas is used, as shown in Fig. 18(a), it was confirmed that there is a tendency for residues of the unexposed resist film to easily occur. Also, in development, when the temperature of the substrate support is 60°C and HBr gas is used, as shown in Fig. 18(b), although the unexposed resist film can be removed, it was confirmed that the difference between the rate of decrease in the thickness of the unexposed resist film and the rate of decrease in the thickness of the exposed resist film can become small. That is, when using HBr gas, it was confirmed that by setting the temperature of the substrate support during development to a high temperature, the unexposed region of the resist film can be removed, but the selectivity in development can become low.

[0169] (Experiment 2)

[0170] In Experiment 2, development of each of the unexposed resist film and the exposed resist film was performed using a processing gas containing only carboxylic acid. In Experiment 2, the pressure of the carboxylic acid, that is, the pressure of the processing gas, was set to 5 Torr (666 Pa). In Experiment 2, the temperature of the substrate support during development was set to 120°C. Also, in Experiment 2, formic acid (H-COOH), trifluoroacetic acid (CF3-COOH), or acetic acid (CH3-COOH) was used as the carboxylic acid.

[0171] Figs. 19(b), 19(c), and 19(d) show the results when formic acid, trifluoroacetic acid, and acetic acid are used as the carboxylic acid, respectively. Note that Fig. 19(a) shows the same results as Fig. 18(b). As shown in these figures, it was confirmed that when using carboxylic acid in development, it is possible to suppress the decrease in the thickness of the exposed resist film even when the temperature of the substrate support is high and obtain a high selectivity. Also, it was confirmed that a particularly high development rate can be obtained when using formic acid or trifluoroacetic acid.

[0172] (Experiment 3)

[0173] In Experiment 3, development was performed on each of an unexposed resist film and an exposed resist film using a processing gas containing only formic acid (H-COOH). In Experiment 3, the pressure of formic acid, i.e., the pressure of the processing gas, was set to 0.5 Torr (66.6 Pa) or 5 Torr (666 Pa). Also, in Experiment 3, the temperature of the substrate support portion during development was set to 60°C, 120°C, or 180°C.

[0174] FIG. 20 shows the results of Experiment 3. When using formic acid, as shown in FIG. 20, it was confirmed that development with a high selectivity ratio is possible at a temperature of 120°C or higher. Also, when using formic acid with the temperature of the substrate support portion being 180°C, it was confirmed that the decrease in the thickness of the exposed resist film is more suppressed compared to the case of using formic acid with the temperature of the substrate support portion being 120°C.

[0175] (Experiment 4)

[0176] In Experiment 4, development was performed on each of an unexposed resist film and an exposed resist film using a processing gas containing only trifluoroacetic acid (CF3-COOH). In Experiment 4, the pressure of trifluoroacetic acid, i.e., the pressure of the processing gas, was set to 0.5 Torr (66.6 Pa) or 5 Torr (666 Pa). Also, in Experiment 4, the temperature of the substrate support portion during development was set to 60°C, 120°C, or 180°C.

[0177] FIG. 21 shows the results of Experiment 4. When using trifluoroacetic acid, as shown in FIG. 21, it was confirmed that development with a high selectivity ratio is possible at a temperature of 120°C or higher. Also, when using trifluoroacetic acid with the temperature of the substrate support portion being 180°C, it was confirmed that the decrease in the thickness of the exposed resist film is more suppressed compared to the case of using trifluoroacetic acid with the temperature of the substrate support portion being 120°C. Also, when using trifluoroacetic acid, it was confirmed that the decrease in the thickness of the exposed resist film is more suppressed compared to the case of using formic acid.

[0178] (Experiment 5)

[0179] In Experiment 5, development was performed on both the unexposed resist film and the exposed resist film using a processing gas containing only acetic acid (CH3 - COOH). In Experiment 5, the pressure of acetic acid, i.e., the pressure of the processing gas, was set to 0.5 Torr (66.6 Pa) or 5 Torr (666 Pa). Also, 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 using acetic acid, as shown in Figure 22, it was confirmed that development with a high selectivity ratio is possible at a temperature of 120°C or higher. Also, when using acetic acid, compared with the case of using formic acid or trifluoroacetic acid, it was confirmed that the decrease in the thickness of the exposed resist film is more suppressed, but the decrease rate of the thickness of the unexposed resist film is relatively low.

[0181] (Experiment 6)

[0182] In Experiment 6, development was performed on both the unexposed resist film and the exposed resist film using a processing gas that is a mixed gas of trifluoroacetic acid (CF3 - COOH) and Ar gas as the processing gas. In Experiment 6, the partial pressure of trifluoroacetic acid was set to 3 Torr (400 Pa). Also, 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 is 90°C, 120°C, and 180°C, respectively. As shown in these figures, when using trifluoroacetic acid, it was confirmed that development capable of selectively removing the unexposed region is possible when the substrate support during development is 90°C or higher.

[0184] (Experiment 7)

[0185] In Experiment 7, development was performed on both the unexposed resist film and the exposed resist film using a processing gas that was a mixed gas of trifluoroacetic acid (CF3-COOH) and Ar gas as the processing gas. In Experiment 7, the temperature of the substrate support during development was set to 120°C. Also, 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 regarding the development of the unexposed resist film, and Figure 24(b) shows the results regarding the development of the exposed resist film. As shown in these figures, when trifluoroacetic acid was used, it was confirmed that development capable of selectively removing the unexposed region was possible by setting the partial pressure of trifluoroacetic acid to 0.36 Torr or more. Also, when trifluoroacetic acid was used, it was confirmed that development with a high selectivity ratio was possible by setting the partial pressure of trifluoroacetic acid to 0.6 Torr or more.

[0187] (Experiment 8)

[0188] In Experiment 8, development was performed on both the unexposed resist film and the exposed resist film using a processing gas that was a mixed gas of acetic acid (CH3-COOH) and Ar gas as the processing gas. In Experiment 8, the temperature of the substrate support during development was set to 120°C, 150°C, 180°C, or 210°C. Also, 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 is used, it was confirmed that development capable of selectively removing the unexposed area is possible by setting the partial pressure of acetic acid to 0.6 Torr or more. Also, when acetic acid is used, it was confirmed that development capable of selectively removing the unexposed area is possible by setting the temperature of the substrate support part to 120°C or more. Further, when acetic acid is used, it was confirmed that the unexposed area can be removed at high speed, that is, a high development speed can be obtained, by setting the temperature of the substrate support part to 180°C or more.

[0190] (Experiment 9)

[0191] In Experiment 9, development of each of the unexposed resist film and the exposed resist film was performed using a processing gas that is a mixed gas of acetic acid (CH3-COOH) and Ar gas as the processing gas. In Experiment 9, the temperature of the substrate support part during development was set to 120°C or 150°C. Also, 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 is used, it was confirmed that development capable of selectively removing the unexposed area is possible by setting the partial pressure of acetic acid in the range of 6 Torr to 60 Torr. Also, when acetic acid is used, it was confirmed that development capable of selectively removing the unexposed area is possible by setting the temperature of the substrate support part to 120°C or more. Further, when acetic acid is used, it was confirmed that the higher the temperature of the substrate support part with the same partial pressure of acetic acid, the more the unexposed area can be removed at high speed, that is, a high development speed can be obtained.

[0193] Here, various exemplary embodiments included in the present disclosure are described in [E1] to [E19] below.

[0194] [E1] (a) A step of providing a substrate on a substrate support portion in a processing chamber, wherein the substrate has an underlying film and a resist film formed from a metal-containing resist provided on the underlying film, and the resist film has a first region and a second region; the above step, (b) A step of supplying a processing gas containing a 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 to dry-develop the resist film; comprising: In the above (b), a substrate processing method, wherein the pressure or partial pressure of the carboxylic acid is 40 Pa or more and less than 13332 Pa.

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

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

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

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

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

[0200] [E7] In the above (b), a substrate processing method according to any one of E1 to E6, wherein the temperature of the substrate support portion is 90 °C or more.

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

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

[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, wherein in (b), the temperature of the substrate support portion 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, wherein in (b), the temperature of the substrate support portion 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, wherein in (b), the temperature of the substrate support portion 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] In (b), (b-1) a step of performing dry development on the resist film under a first condition; (b-2) a step of performing dry development on the resist film under a second condition different from the first condition; and The combination of the first condition and the second condition satisfies one or more of condition (A), condition (B), and condition (C). Condition (A) includes developing the resist using a first processing gas in (b-1) and developing the resist film using a second processing gas different from the first processing gas in (b-2). In this condition (A), at least one of the first processing gas and the second processing gas contains the carboxylic acid. Condition (B) includes developing the resist film by setting the pressure of the carboxylic acid to a first pressure in (b-1) and developing the resist film by setting the pressure of the carboxylic acid to a second pressure different from the first pressure in (b-2). Condition (C) includes developing the resist film by setting the substrate support part to a first temperature in (b-1) and developing the resist film by setting the substrate support part to a second temperature different from the first temperature in (b-2). 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. The combination of the processing conditions in the first period and the processing conditions in the second period satisfies one or more of condition (A), condition (B), and condition (C). Condition (A) includes developing the resist film using a first processing gas in the first period and developing the resist film using a second processing gas different from the first processing gas in the second period. In this condition (A), at least one of the first processing gas and the second processing gas contains the carboxylic acid. Condition (B) includes developing the resist film by setting the pressure of the carboxylic acid to a first pressure in the first period and developing the resist film by setting the pressure of the carboxylic acid to a second pressure different from the first pressure in the second period. Condition (C) includes developing the resist film by setting the temperature of the substrate support portion to a first temperature in the first period, and developing the resist film by setting the temperature of the substrate support portion to a second temperature different from the first temperature in 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), a step of forming a deposited film on the first region; A step of removing the residue generated in (b) while protecting the first region with the deposited film; A step of removing the remaining portion of the second region; The substrate processing method according to any one of E1 to E13, further including the above steps.

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

[0211] [E18] In (b), the second region is partially removed. The substrate processing method includes: After (b), a step of heating the substrate; A step of removing the remaining portion of the second region; The substrate processing method according to any one of E1 to E13, further including the above steps.

[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. Further, in the embodiment of E18, the temperature of the substrate in the step of heating the substrate may be 240°C or lower, or 220°C or lower. Further, in the embodiment of E18, the step of heating the substrate and the step of removing the remainder 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 in the step of removing the remainder may be the same chamber, i.e., a single chamber, or may be different chambers from each other.

[0213] [E19] A processing chamber, a substrate support portion provided in the processing chamber, a gas supply portion configured to supply a processing gas containing a carboxylic acid into the chamber, an exhaust mechanism connected to the processing chamber, a control unit, and the control unit is configured to control the gas supply portion and the exhaust mechanism so as to supply the processing gas into the chamber to adjust the pressure or partial pressure of the carboxylic acid to 40 Pa or more and less than 13332 Pa for dry development of the resist film on the substrate placed on the substrate support portion. A substrate processing system.

[0214] From the above description, it will be understood that the various embodiments of the present disclosure are described herein for the purpose of explanation, and various changes can be made without departing from the scope and gist of the present disclosure. Therefore, the various embodiments disclosed herein are not intended to be limiting, and the true scope and gist are indicated by the appended claims.

Description of Reference Numerals

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

Claims

1. (a) A step of providing a substrate on a substrate support portion in a processing chamber, wherein the substrate has an underlying film and a resist film formed from a metal-containing resist provided on the underlying film, and the resist film has a first region and a second region; the step as described above, (b) Supplying a processing gas containing a 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 to dry-develop the resist film; the step as described above, including, the resist film is a resist film containing tin oxide, the carboxylic acid is formic acid, trifluoroacetic acid, or acetic acid, in the step (b), the pressure or partial pressure of the carboxylic acid is 40 Pa or more and less than 13332 Pa, A substrate processing method.

2. In the step (b), the pressure or partial pressure of the carboxylic acid is 133 Pa or more. The substrate processing method according to Claim 1.

3. In the step (b), the pressure or partial pressure of the carboxylic acid is 666 Pa or more. The substrate processing method according to Claim 1.

4. In the step (b), the pressure or partial pressure of the carboxylic acid is 1333 Pa or less. The substrate processing method according to Claim 1.

5. The processing gas contains an inert gas. In the step (b), the partial pressure of the carboxylic acid is 40 Pa or more. The substrate processing method according to Claim 1.

6. The partial pressure of the carboxylic acid is 8000 Pa or less. The substrate processing method according to Claim 5.

7. In the step (b), the temperature of the substrate support portion is 90 °C or more. The substrate processing method according to Claim 1.

8. In the above (b), the temperature of the substrate support is 120°C or higher. The substrate processing method according to claim 1.

9. In the above (b), the temperature of the substrate support is 300°C or lower. The substrate processing method according to claim 1.

10. The carboxylic acid is the formic acid, In the above (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 claim 1.

11. The carboxylic acid is the trifluoroacetic acid, In the above (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 claim 1.

12. The carboxylic acid is the acetic acid, In the above (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 claim 1.

13. The above (b) is (b-1) A step of performing dry development on the resist film under a first condition; (b-2) A step of performing dry development on the resist film under a second condition different from the first condition; including The combination of the first condition and the second condition satisfies one or more of condition (A), condition (B), and condition (C), Condition (A) includes developing the resist using a first processing gas in the above (b-1) and developing the resist film using a second processing gas different from the first processing gas in the above (b-2). In this condition (A), at least one of the first processing gas and the second processing gas contains the carboxylic acid. Condition (B) includes developing the resist film by setting the pressure of the carboxylic acid to a first pressure in (b-1) and developing the resist film by setting the pressure of the carboxylic acid to a second pressure different from the first pressure in (b-2). Condition (C) includes developing the resist film by setting the substrate support part to a first temperature in (b-1) and developing the resist film by setting the substrate support part to a second temperature different from the first temperature in (b-2). The substrate processing method according to any one of claims 1 to 12.

14. The period during which (b) is performed includes a first period and a second period alternating with the first period. The combination of the processing conditions in the first period and the processing conditions in the second period satisfies one or more of condition (A), condition (B), and condition (C). Condition (A) includes developing the resist film using a first processing gas in the first period and developing the resist film using a second processing gas different from the first processing gas in the second period. In this condition (A), at least one of the first processing gas and the second processing gas contains the carboxylic acid. Condition (B) includes developing the resist film by setting the pressure of the carboxylic acid to a first pressure in the first period and developing the resist film by setting the pressure of the carboxylic acid to a second pressure different from the first pressure in the second period. Condition (C) includes developing the resist film by setting the temperature of the substrate support part to a first temperature in the first period and developing the resist film by setting the temperature of the substrate support part to a second temperature different from the first temperature in the second period. The substrate processing method according to any one of claims 1 to 12.

15. In (b), the second region is partially removed. The substrate processing method is as follows. After the step (b), a step of forming a deposited film on the first region; A step of removing the residue generated in the step (b) while protecting the first region with the deposited film; A step of removing the remaining portion of the second region; The substrate processing method according to any one of claims 1 to 12, further comprising the above steps.

16. The deposited film is a carbon-containing film or a silicon-containing film, The residue is removed by plasma of a processing gas containing at least one selected from the group consisting of a helium-containing gas, a hydrogen-containing gas, a bromine-containing gas, and a chlorine-containing gas. The substrate processing method according to claim 15.

17. In the step (b), the second region is partially removed, The substrate processing method includes: After the step (b), a step of heating the substrate; A step of removing the remaining portion of the second region; The substrate processing method according to any one of claims 1 to 12, further comprising the above steps.

18. A processing chamber; A substrate support portion provided in the processing chamber; A gas supply portion configured to supply a processing gas containing a carboxylic acid that is formic acid, trifluoroacetic acid, or acetic acid into the chamber; An exhaust mechanism connected to the processing chamber; A control unit; Comprising: The control unit is configured to control the gas supply portion and the exhaust mechanism so as to supply the processing gas into the chamber to adjust the pressure or partial pressure of the carboxylic acid to 40 Pa or more and less than 13332 Pa for dry development of a resist film containing tin oxide on a substrate placed on the substrate support portion. A substrate processing system.

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