Substrate processing method and substrate processing system

Abstract

The invention provides a substrate processing method. The substrate processing method includes (a) providing a substrate having a base film and a resist film provided on the base film and formed of a metal-containing resist on a substrate support portion in a processing chamber, in which the metal-containing resist has a first region and a second region. The substrate processing method further includes a step (b) 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, thereby performing dry development on the resist film. In (b), the pressure or partial pressure of the carboxylic acid is at least 0.3 Torr (40Pa) and less than 100 Torr (13332 Pa).

Description

[0001] Cross-references to related patent applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 393,377, filed on July 29, 2022, entitled “SUBSTRATE TREATMENT METHOD AND SUBSTRATE TREATMENT SYSTEM,” and is incorporated herein by reference in its entirety. Technical Field

[0003] Exemplary embodiments of the present invention relate to a substrate processing method and a substrate processing system. Background Art

[0004] Patent Document 1 discloses a technique for forming a thin film patterned on a semiconductor substrate using extreme ultraviolet light (hereinafter referred to as “EUV”).

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application No. 2021-523403 Summary of the invention

[0008] Technical issues to be solved by the invention

[0009] The present invention provides a technique for appropriately dry developing an exposed metal-containing resist.

[0010] Means for solving technical problems

[0011] In an exemplary embodiment of the present invention, a substrate processing method is provided. The substrate processing method includes the following steps: (a) providing a substrate having a base film and a resist film disposed on the base film and formed by a metal-containing resist on a substrate support portion in a processing chamber, wherein the metal-containing resist has a first region and a second region. The substrate processing method also includes the following steps: (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 relative to the first region, thereby dry developing the resist film. In (b), the pressure or partial pressure of the carboxylic acid is greater than 0.3 Torr (40 Pa) and less than 100 Torr (13332 Pa).

[0012] Effects of the Invention

[0013] According to an exemplary embodiment of the present invention, a technique for appropriately dry-developing an exposed metal-containing resist can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a diagram for explaining a configuration example of a heat treatment system.

[0015] Figure 2 It is a diagram for explaining a configuration example of a plasma processing system.

[0016] Figure 3 It is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0017] Figure 4 This is a flowchart showing the substrate processing method according to the first embodiment.

[0018] Figure 5 It means in Figure 4 FIG. 2 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11 of the substrate processing method shown.

[0019] Figure 6 FIG. 1 is a diagram showing an example of a base film UF of a substrate W. FIG.

[0020] Figure 7 FIG. 1 is a diagram showing an example of a base film UF of a substrate W. FIG.

[0021] Figure 8 1 is a diagram showing an example of a cross-sectional structure of the substrate W after development.

[0022] Fig. 9 This is a flowchart showing a substrate processing method according to the second embodiment.

[0023] Fig.10 (a) Fig.10 (b) and Fig.10 (c) are each a timing chart showing an example of the substrate processing method according to the third embodiment.

[0024] Fig.11 This is a flowchart showing a substrate processing method according to the fourth embodiment.

[0025] Fig.12 (a) and Fig.12 (b) are diagrams each showing an example of a cross-sectional structure of the substrate W after being processed in step ST42.

[0026] Fig.13 (a) is a diagram showing an example of a cross-sectional structure of a substrate W after processing in step ST43. Fig.13 (b) is a diagram showing an example of a cross-sectional structure of the substrate W after being processed in step ST45.

[0027] Fig.14(a) is a schematic cross-sectional view showing another configuration example of the heat treatment system, Fig.14 (b) is a schematic plan view showing another configuration example of the heat treatment system.

[0028] Fig.15 It is a schematic diagram showing a configuration example of a substrate support portion.

[0029] Fig.16 It is a block diagram for explaining a configuration example of a substrate processing system SS.

[0030] Fig.17 is a flow chart representing method MT.

[0031] Fig.18 (a) and Fig.18 (b) are graphs showing experimental results.

[0032] Fig.19 (a)~ Fig.19 (d) are graphs showing experimental results.

[0033] Fig. 20 It is a graph showing the experimental results.

[0034] Fig.21 It is a graph showing the experimental results.

[0035] Fig. 22 It is a graph showing the experimental results.

[0036] Fig.23 (a)~ Fig.23 (c) are graphs showing experimental results.

[0037] Fig.24 (a) and Fig.24 (b) are graphs showing experimental results.

[0038] Fig.25 It is a graph showing the experimental results.

[0039] Fig.26 It is a graph showing the experimental results. DETAILED DESCRIPTION

[0040] A substrate processing method according to an exemplary embodiment of the present invention includes the following steps: (a) providing a substrate having a base film and a resist film formed of a metal-containing resist disposed on the base film on a substrate support portion in a processing chamber, wherein the metal-containing resist has a first region and a second region. The substrate processing method also includes the following steps: (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 relative to the first region, thereby dry developing the resist film. In (b), the pressure or partial pressure of the carboxylic acid is greater than 0.3 Torr (40 Pa) and less than 100 Torr (13332 Pa).

[0041] Hereinafter, various embodiments of the present invention will be described in detail with reference to the accompanying drawings. In addition, in each of the accompanying drawings, the same symbols are marked for the same or similar elements, and repeated 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 accompanying drawings. The dimensional ratios of the accompanying drawings do not represent the actual ratios, and the actual ratios are not limited to the ratios shown in the drawings.

[0042] <Configuration example of heat treatment system>

[0043] Figure 1 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 treatment system, and the heat treatment apparatus 100 is an example of a substrate treatment apparatus.

[0044] 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 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 top heater 130 is provided on the top wall (top plate) of the processing chamber 102. The top surface 140 of the top wall (top plate) of the processing chamber 102 is formed as a horizontal flat surface, and its temperature is adjusted by the top heater 130.

[0045] A substrate support portion 121 is provided at the lower side in the processing chamber 102. The substrate support portion 121 constitutes a loading portion on which the substrate W is loaded. The substrate support portion 121 is formed in a circular shape, for example, when viewed from above, and the substrate W is loaded on its surface (upper surface) formed horizontally. A workbench heater 120 is embedded in the substrate support portion 121. The workbench heater 120 can heat the substrate W loaded on the substrate support portion 121. In addition, a ring assembly (not shown) can be arranged on the substrate support portion 121 in a manner surrounding the substrate W. The ring assembly can include one or more annular components. By arranging the ring assembly around the substrate W, the temperature controllability of the peripheral area of ​​the substrate W can be improved. The ring assembly can be composed of an inorganic material or an organic material depending on the target heat treatment.

[0046] The substrate support part 121 is supported in the processing chamber 102 by a support 122 provided on the bottom surface of the processing chamber 102. A plurality of lifting pins 123 capable of vertical lifting and lowering are provided on the outer side of the support 122 in the circumferential direction. The plurality of lifting pins 123 are respectively inserted into through holes provided in the substrate support part 121. The plurality of lifting pins 123 are arranged at intervals in the circumferential direction. The lifting and lowering action of the plurality of lifting pins 123 is realized by a lifting mechanism 124. If the lifting pins 123 protrude toward the surface of the substrate support part 121, the substrate W can be transferred between the conveying mechanism (not shown) and the substrate support part 121.

[0047] An exhaust port 131 having an opening is provided on the side wall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump and a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. By adjusting the exhaust flow rate based on the exhaust mechanism 132, the pressure in the processing chamber 102 is adjusted. In addition, a transfer port for a substrate W (not shown) is formed on the side wall of the processing chamber 102 in a manner that can be opened and closed at a position different from the position where the exhaust port 131 opens.

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

[0049] The gas nozzle 141 is formed in a rod shape protruding from the side wall of the processing chamber 102 toward the center of the processing chamber 102. The front end of the gas nozzle 141 extends horizontally from the side wall of the processing chamber 102. The processing gas is ejected into the processing chamber 102 from the ejection port opened at the front end of the gas nozzle 141, and the gas is ejected along the gas nozzle 141. Figure 1 The gas flows in the direction of the dashed arrow and is exhausted from the exhaust port 131. The front end of the gas nozzle 141 may extend obliquely downward toward the substrate W or may extend obliquely upward toward the top surface 140 of the processing chamber 102.

[0050] In addition, the gas nozzle 141 may be disposed on, for example, a top wall of the processing chamber 102 . Also, the exhaust port 131 may be disposed on a bottom surface of the processing chamber 102 .

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

[0052] The control unit 200 processes computer executable commands that cause the heat treatment device 100 to perform various processes described in the present invention. The control unit 200 can be configured to control the various elements of the heat treatment device 100 in a manner that performs various processes described herein. In one embodiment, a part or all of the control unit 200 may also be included in the heat treatment device 100. The control unit 200 may also include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3. The control unit 200 may be implemented, for example, by a computer 200a. The processing unit 200a1 may be configured to perform various control actions by reading a program from the storage unit 200a2 and executing the read program. The program may be stored in the storage unit 200a2 in advance, and may also be obtained via a medium when necessary. The obtained program is stored in the storage unit 200a2, and is read and executed from the storage unit 200a2 by the processing unit 200a1. The medium can be various storage media readable by the computer 200a, or it can be a communication line connected to the communication interface 200a3. The processing unit 200a1 can also be a CPU (Central Processing Unit). The storage unit 200a2 can also include RAM (Random Access Memory), ROM (Read Only Memory), HDD (Hard Disk Drive), SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 can also communicate with the heat treatment device 100 via a communication line such as a LAN (Local Area Network).

[0053] <Configuration example of plasma processing system>

[0054] Figure 21 is a diagram illustrating an example of a configuration when a plasma processing system is used as a developing processing system. In one embodiment, the plasma processing system includes a plasma processing device 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing device 1 is an example of a substrate processing device. The plasma processing device 1 includes a plasma processing chamber (hereinafter referred to as a "processing chamber") 10, a substrate support portion 11, and a plasma generating portion 12. The plasma processing chamber 10 has a plasma processing space. In addition, 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 exhaust port for exhausting the gas from the plasma processing space. The gas supply port is connected to the gas supply portion 20 described later, and the gas exhaust port is connected to the exhaust system 40 described later. The substrate support portion 11 is arranged in the plasma processing space, and has a substrate supporting surface for supporting a substrate.

[0055] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may also be a capacitively coupled plasma (CCP; Capacitively Coupled Plasma), an inductively coupled plasma (ICP; Inductively Coupled Plasma), an ECR plasma (Electron-Cyclotron-resonance plasma, electron cyclotron resonance plasma), a helicon wave excited plasma (HWP: Helicon Wave Plasma), or a surface wave plasma (SWP: Surface Wave Plasma), etc. In addition, various types of plasma generating units including an AC (Alternating Current: alternating current) plasma generating unit and a DC (Direct Current: direct current) plasma generating unit may be used. In one embodiment, the AC signal (AC power) used in the AC plasma generating unit has a frequency in the range of 100kHz to 10GHz. Therefore, the AC signal includes an RF (Radio Frequency: radio frequency) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100kHz to 150MHz.

[0056] The control unit 2 processes computer executable commands that cause the plasma processing device 1 to execute the various processes described in the present invention. The control unit 2 can be configured to control the various elements of the plasma processing device 1 in a manner that executes the various processes described herein. In one embodiment, a part or all of the control unit 2 can also be included in the plasma processing device 1. The control unit 2 can be implemented, for example, by a computer 2a. The control unit 2 can also include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. The various structures of the control unit 2 can be combined with the above-mentioned control unit 200 (see Figure 1 ) have the same structures.

[0057] Hereinafter, a configuration example of a capacitive coupling type plasma processing apparatus will be described as an example of the plasma processing apparatus 1 . Figure 3 It is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0058] A capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power supply 30, and an exhaust system 40. Furthermore, the plasma processing apparatus 1 includes a substrate support unit 11 and a gas inlet unit. The gas inlet unit is configured to introduce at least one processing gas into the plasma processing chamber 10. The gas inlet 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 portion 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 shell of the plasma processing chamber 10.

[0059] The substrate support portion 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central area 111a for supporting a substrate W and an annular area 111b for supporting the ring assembly 112. A wafer is an example of a substrate W. The annular area 111b of the main body 111 surrounds the central area 111a of the main body 111 when viewed from above. The substrate W is arranged on the central area 111a of the main body 111, and the ring assembly 112 is arranged on the annular area 111b of the main body 111 in a manner of surrounding the substrate W on the central area 111a of the main body 111. Therefore, the central area 111a is also referred to as a substrate supporting surface for supporting the substrate W, and the annular area 111b is also referred to as a ring supporting surface for supporting the ring assembly 112.

[0060] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive component. The conductive component of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is arranged on the base 1110. The electrostatic chuck 1111 includes a ceramic component 1111a and an electrostatic electrode 1111b arranged in the ceramic component 1111a. The ceramic component 1111a has a central area 111a. In one embodiment, the ceramic component 1111a also has an annular area 111b. In addition, other components surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating component, may also have an annular area 111b. At this time, the ring assembly 112 may be arranged on the annular electrostatic chuck or the annular insulating component, or on both the electrostatic chuck 1111 and the annular insulating component. Furthermore, at least one RF / DC electrode combined with the RF power supply 31 and / or the DC power supply 32 described later can be arranged in the ceramic component 1111a. In this case, at least one RF / DC electrode functions as a lower electrode. In the case where the bias RF signal and / or 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. In addition, the conductive component of the base 1110 and at least one RF / DC electrode can function as multiple lower electrodes. Furthermore, the electrostatic electrode 1111b can function as a lower electrode. Therefore, the substrate support portion 11 includes at least one lower electrode.

[0061] The ring assembly 112 includes one or more ring-shaped components. In one embodiment, the one or more ring-shaped components 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.

[0062] Furthermore, the substrate support portion 11 may also include a temperature adjustment module, which is configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature adjustment module may also include a heater, a heat transfer medium, a flow path 1110a, or a combination thereof. A heat transfer fluid such as salt water 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 arranged in the ceramic component 1111a of the electrostatic chuck 1111. Furthermore, the substrate support portion 11 may also include a heat transfer gas supply portion, which is configured to supply a heat transfer gas to the gap between the back side of the substrate W and the central area 111a.

[0063] The showerhead 13 is configured to introduce at least one processing gas from the gas supply part 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and a plurality of gas introduction ports 13c. The processing gas supplied to the gas supply port 13a is introduced into the plasma processing space 10s from the plurality of gas introduction ports 13c through the gas diffusion chamber 13b. In addition, the showerhead 13 includes at least one upper electrode. In addition, in addition to the showerhead 13, the gas introduction part may also include one or more side gas injection parts (SGI: Side Gas Injector) installed in one or more openings formed in the side wall 10a.

[0064] The gas supply unit 20 may also 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 processing gas from each corresponding gas source 21 to the nozzle 13 via each corresponding flow controller 22. Each flow controller 22 may also include, for example, a mass flow controller or a pressure-controlled flow controller. In addition, the gas supply unit 20 may also include at least one flow modulation device for modulating or pulsing the flow of at least one processing gas.

[0065] 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. Thus, plasma is formed by at least one processing gas supplied to the plasma processing space 10s. Therefore, the RF power supply 31 can function as at least a part of the plasma generating unit 12. Furthermore, by supplying a bias RF signal to at least one lower electrode, a bias potential can be generated on the substrate W, and ion components in the formed plasma can be introduced into the substrate W.

[0066] In one embodiment, the RF power supply 31 includes a first RF generator 31a and a second RF generator 31b. The first RF generator 31a is configured to be coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit, and 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 generator 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.

[0067] The second RF generating unit 31b is configured to be coupled to at least one lower electrode via at least one impedance matching circuit, and 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 that of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF generating unit 31b may be configured to generate a plurality of bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. Furthermore, in various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0068] In addition, the power supply 30 may include a DC power supply 32 combined with the plasma processing chamber 10. The DC power supply 32 includes a first DC generating unit 32a and a second DC generating unit 32b. In one embodiment, the first DC generating unit 32a is configured to be connected to at least one lower electrode and generate a first DC signal. The generated first DC signal is applied to at least one lower electrode. In one embodiment, the second DC generating unit 32b is configured to be connected to at least one upper electrode and generate a second DC signal. The generated second DC signal is applied to at least one upper electrode.

[0069] 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 pulse may have a pulse waveform of a rectangle, a trapezoid, a triangle, or a combination thereof. In one embodiment, a waveform generator for generating a sequence of voltage pulses from a DC signal is connected between the first DC generator 32a and at least one lower electrode. Therefore, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. In the case where the second DC generator 32b and the waveform generator constitute a voltage pulse generator, the voltage pulse generator is connected to at least one upper electrode. The voltage pulse may have a positive polarity or a negative polarity. Furthermore, the sequence of voltage pulses may include one or more positive polarity voltage pulses and one or more negative polarity voltage pulses in one cycle. In addition, the first and second DC generators 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generator 32a may be provided instead of the second RF generator 31b.

[0070] The exhaust system 40 may be connected to a gas outlet 10e provided at the bottom of the plasma processing chamber 10, for example. The exhaust system 40 may also 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 also include a turbomolecular pump, a dry pump, or a combination thereof.

[0071] <Substrate processing method>

[0072] Hereinafter, various embodiments of the substrate processing method according to the present invention will be described.

[0073] [First embodiment]

[0074] Figure 4 1 is a flowchart showing a substrate processing method according to the first embodiment (hereinafter also referred to as “method MT1”). Figure 4 As shown, method MT1 includes step ST11 of providing a substrate and step ST12 of developing the substrate. In one embodiment, the development process in step ST12 is performed by a dry process using a processing gas (hereinafter also referred to as "dry development").

[0075] Method MT1 can use the substrate processing system described above (refer to Figure 1 to Figure 3 ), or two or more of these substrate processing systems. For example, method MT1 may be performed in a thermal processing system (reference Figure 1 ) is executed. Hereinafter, the method MT1 will be described by taking the case where the control unit 200 controls each unit of the heat treatment apparatus 100 and applies the method MT1 to the substrate W as an example.

[0076] (Step ST11: Providing a Substrate)

[0077] First, in step ST11, a substrate W is provided in a processing chamber 102 of a heat treatment apparatus 100. The substrate W is provided on a substrate support portion 121 via lift pins 123. After the substrate W is arranged 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 can also be performed by controlling the output of one or more heaters among the side wall heater 104, the workbench heater 120, the top heater 130 and the piping heater 160 (hereinafter collectively referred to as "each heater"). In method MT1, the temperature of the substrate support portion 121 can be adjusted to a set temperature before step ST11. That is, the substrate W can be provided on the substrate support portion 121 after the temperature of the substrate support portion 121 is adjusted to the set temperature.

[0078] Figure 5 It means in Figure 4 FIG. 1 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11 of the substrate processing method shown in FIG. The substrate W includes a base film UF and a resist film RM formed on the base film UF. The substrate W can be used for manufacturing semiconductor devices. The semiconductor devices include memory devices such as DRAM and 3D-NAND flash memory and logic devices.

[0079] The resist film RM is a metal-containing resist film containing a metal. In one example, the metal may include at least one metal selected from the group consisting of Sn, Hf, and Ti. In one example, the resist film RM contains Sn and may include tin oxide (SnO bond) and tin hydroxide (Sn-OH bond). The resist film RM may also include an organic substance.

[0080] like Figure 5 As shown, the resist film RM has an exposed first region RM1 and an unexposed second region RM2. The first region RM1 is a region exposed to EUV light, i.e., an EUV exposed region. The second region RM2 is a region not exposed to EUV light, i.e., an unexposed region.

[0081] The base film UF may be an organic film, a dielectric film, a metal film, a semiconductor film, or a stacked film thereof formed on a silicon wafer.

[0082] Figure 6 and Figure 7 Each of them is a diagram showing an example of a base film UF of a substrate W. Figure 6 As shown, the base film UF can be composed of a first film UF1, a second film UF2 and a third film UF3. Figure 7 As shown, the base film UF can be composed of the second film UF2 and the third film UF3.

[0083] The first film UF1 is, for example, a spin-on glass (SOG) film, a SiC film, a SiON film, a Si-containing anti-reflection 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 nitride oxide film, a silicon carbon nitride film, a polycrystalline silicon film or a carbon-containing silicon film. The third film UF3 can be composed of a plurality of types of stacked silicon-containing films. For example, the third film UF3 can be composed of alternately stacked silicon oxide films and silicon nitride films. Furthermore, the third film UF3 can be composed of alternately stacked silicon oxide films and polycrystalline silicon films. Furthermore, the third film UF3 can be a stacked film including a silicon nitride film, a silicon oxide film and a polycrystalline silicon film. Furthermore, the third film UF3 can be composed of stacked silicon oxide films and silicon carbon nitride films. Furthermore, the third film UF3 may be a stacked film including a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.

[0084] In one embodiment, the substrate W is formed as follows. First, a photoresist film containing a metal is formed on a base film to which a treatment for improving adhesion has been applied. The film formation may be performed in a dry process, in a wet process such as a solution coating method, or in both a dry process and a wet process. In addition, a surface modification treatment of the base film may be performed before the formation of the photoresist film. The substrate after the formation of the photoresist film is subjected to a heating treatment, i.e., a pre-bake (Post Apply Bake: PAB). An additional heating treatment may also be performed on the pre-baked substrate. The substrate after the heating treatment is transported to an exposure device, and the photoresist film is irradiated with EUV light via an exposure mask (intermediate mask). Thus, a substrate W including a base 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 (intermediate mask). The second region RM2 is a region corresponding to a pattern provided in the exposure mask (intermediate mask). EUV light has a wavelength in the range of 10 to 20 nm, for example. EUV light can have a wavelength in the range of 11 to 14 nm, and in one example has a wavelength of 13.5 nm. The exposed substrate W is transported from the exposure device to the heat treatment device under atmosphere management, and undergoes a heat treatment, namely, post-exposure baking (PEB). Additional heat treatment can also be performed on the substrate W after PEB.

[0085] (Step ST12: Development of Substrate)

[0086] Next, in step ST12 , the second region RM2 of the substrate W is selectively removed by exposing the substrate W to the processing gas, and the resist film RM is developed.

[0087] In step ST12, a processing gas is supplied into the processing chamber 102 via a 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 as the halogen element, fluorine and / or chlorine may be contained. The fluorine-containing carboxylic acid may be, for example, at least one selected from the group consisting of monofluoroacetic acid (CFH2COOH), difluoroacetic acid (CF2HCOOH), and trifluoroacetic acid (CF3COOH), or trifluoroacetic acid. The chlorine-containing carboxylic acid may be, for example, at least one selected from the group consisting of monochloroacetic acid (CClH2COOH), dichloroacetic acid (CCl2HCOOH), and trifluoroacetic acid (CCl3COOH). The fluorine- and chlorine-containing carboxylic acid may be, for example, fluorochloroacetic 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, or may be formic acid and / or trifluoroacetic acid, or may be trifluoroacetic acid.

[0088] The processing gas may also contain an inert gas. The inert gas may be nitrogen or a rare gas such as Ar. In addition, the processing gas may contain an inorganic acid in addition to the inert gas, or an organic acid other than carboxylic acid. In addition, the processing gas may contain an oxidizing gas such as O2 gas and / or CO2 gas.

[0089] Furthermore, 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. In the case where 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. In the case where 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 are sometimes 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 to the processing chamber 102 and / or the flow rate of the carboxylic acid discharged from the processing chamber 102. In the case where 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 to the processing chamber 102 and the flow rate of the gas other than the carboxylic acid and / or the flow rate of the carboxylic acid gas discharged from the processing chamber 102 and the flow rate of the gas other than the carboxylic acid.

[0090] 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, or 5 Torr (666 Pa) or more. In addition, the partial pressure of the carboxylic acid may be less than 100 Torr (13332 Pa), 90 Torr (12000 Pa) or less, 80 Torr (13332 Pa) or less, 70 Torr (9333 Pa) or less, 60 Torr (8000 Pa) or less, or 10 Torr (1333 Pa) or less. In one embodiment, the pressure of the carboxylic acid may be 1 Torr or more and less than 100 Torr. When the pressure of the carboxylic acid is 1 Torr or more, a higher development speed can be achieved, and a higher throughput can be achieved. On the other hand, when the pressure of the carboxylic acid is less than 100 Torr, a higher development speed and a higher development contrast (selectivity) can be achieved.

[0091] Furthermore, in step ST12, the temperature of the substrate W or the substrate support 121 can be controlled. In one embodiment, the temperature of the substrate support 121 in step ST12 can be above -20°C, above 0°C, above 20°C, above 90°C, or above 120°C. Furthermore, the temperature of the substrate support 121 in step ST12 can be below 300°C, below 220°C, below 210°C, or below 200°C. In one embodiment, the temperature of the substrate support 121 is controlled to be above -20°C and below 220°C. If the temperature of the substrate support 121 is above 0°C, the decrease in the development speed can be suppressed. On the other hand, if the temperature of the substrate support 121 is less than 200°C, a high development speed and a high development contrast (selection ratio) can be achieved. The temperature of the substrate support 121 can be controlled by the power supplied to the workbench heater 120. Furthermore, the temperature of the substrate support portion 121 can be controlled by the power supplied to the side wall heater 104 and / or the top heater 130 together with the stage heater 120 or instead of the stage heater 120. Furthermore, the temperature of the substrate support portion 121 can be controlled by an infrared lamp or microwave, etc. together with the power supplied to the above-mentioned heaters or instead of the power supplied to the above-mentioned heaters.

[0092] In step ST12, when the carboxylic acid in the process gas is formic acid, the temperature of the substrate support part 121 may be 120° C. or more. In step ST12, when the carboxylic acid in the process gas is formic acid, the pressure of the carboxylic acid may be 0.3 Torr or more or 0.5 Torr or more. In step ST12, when the carboxylic acid in the process gas is trifluoroacetic acid, the temperature of the substrate support part 121 may be 90° C. or more or 120° C. or more. In step ST12, when the carboxylic acid in the process gas is trifluoroacetic acid, the pressure of the carboxylic acid may be 0.3 Torr or more or 0.5 Torr or more. In step ST12, when the carboxylic acid in the process gas is acetic acid, the temperature of the substrate support part 121 may be 120° C. or more, 150° C. or more, or 180° C. or more. In step ST12, when the carboxylic acid in the process gas is acetic acid, the pressure of the carboxylic acid may be 0.3 Torr or more or 0.5 Torr or more.

[0093] The step ST12 may be performed to remove the second region RM2 until the base film UF is exposed. Figure 8 FIG. 1 is a diagram showing an example of a cross-sectional structure of a substrate W after development. Figure 8 In the example shown, 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 of the first region RM1. The opening OP is a space surrounded by the side on the base film UF. In a top view of the substrate W, the opening OP has a shape corresponding to the second region RM2 (a shape that ultimately corresponds to the exposure mask pattern for EUV exposure). The shape can be, for example, a circle, an ellipse, a rectangle, a line, or a combination of one or more of these shapes. A plurality of openings OP can be provided on the developed resist film RM. A plurality of openings OP can each have a line shape, and can be arranged at a specified interval to form a pattern of lines and intervals. Furthermore, a plurality of openings OP can also be arranged in a grid shape to form a columnar pattern.

[0094] According to the first embodiment, the second region RM2 can be removed with a high selectivity (ratio of the development speed of the second region RM2 to the development speed of the first region RM1, hereinafter also referred to as "development contrast") relative to the first region RM1. Furthermore, according to the first embodiment, the generation of residues due to development can be suppressed.

[0095] Next, a substrate processing method according to another embodiment of the present invention will be described. In addition, in the following description, portions overlapping with the first embodiment are simplified or omitted.

[0096] [Second embodiment]

[0097] Fig. 91 is a flowchart showing a substrate processing method according to the second embodiment (hereinafter also referred to as "method MT2"). Method MT2 includes steps ST21 and ST22. In step ST21, a substrate W is provided in the same manner as step ST11 of method MT1. In the next step ST22, the resist film RM is developed. Step ST22 includes step ST22-1 for developing a portion of the resist film under a first condition, and step ST22-2 for developing the resist film RM under a second condition different from the first condition.

[0098] 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), or any two or more. In addition, in the following description, when the processing gas is a single gas, the pressure of the carboxylic acid refers to the pressure of the carboxylic acid, and when the processing gas is a mixed gas, it refers to the partial pressure of the carboxylic acid.

[0099] In step (A) ST22-1, the resist film RM is developed using a first process gas, and in step ST22-2, the resist film RM is developed using a second process gas different from the first process gas.

[0100] In step (B) ST22-1, the pressure of the carboxylic acid is set to a first pressure to develop the resist film RM, and in step ST22-2, the pressure of the carboxylic acid is set to a second pressure different from the first pressure to develop the resist film RM.

[0101] In step (C) ST22 - 1 , the substrate supporting portion 121 is set to a first temperature to develop the resist film RM, and in step ST22 - 2 , the substrate supporting portion 121 is set to a second temperature different from the first temperature to develop the resist film RM.

[0102] In an example satisfying condition (A), a gas containing an inorganic acid may be used as the first process gas, and a gas containing a carboxylic acid may be used as the second process gas. The inorganic acid may be a gas having 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-mentioned carboxylic acids.

[0103] In another example satisfying condition (A), a gas containing an organic acid other than carboxylic acid may be used as the first process gas, and a gas containing carboxylic acid may be used as the second process gas. Alternatively, a gas containing carboxylic acid may be used as the first process gas, and a gas containing an organic acid other than carboxylic acid may be used as the second process gas. Alternatively, a gas containing carboxylic acid may be used as the first process gas, and a carboxylic acid having an acidity lower than that of the first process gas or a gas containing an organic acid other than carboxylic acid may be used as the second process gas. Organic acids other than carboxylic acids may be β-dicarbonyl compounds 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), or alcohols such as nonafluorotert-butyl alcohol ((CF3)3C-OH). Carboxylic acids may be any one or more of the above-mentioned carboxylic acids.

[0104] In another example satisfying condition (A), a gas containing a first carboxylic acid may be used as the first process gas, and a gas containing a second carboxylic acid different from the first carboxylic acid may be used as the second process gas. The acidity of the second carboxylic acid may be lower than the acidity of the first carboxylic acid. Trifluoroacetic acid may be used as the first carboxylic acid, and formic acid or acetic acid may be used as the second carboxylic acid, or formic acid may be used as the first carboxylic acid, and acetic acid may be used as the second carboxylic acid.

[0105] In an example satisfying condition (B), a mixed gas containing carboxylic acid can be used as the processing gas. For example, the processing gas contains carboxylic acid and an inert gas. At this time, in step ST22-1, the partial pressure of the carboxylic acid can be set to a first pressure, and in step ST22-2, the partial pressure of the carboxylic acid can be set to a second pressure different from the first pressure. The second pressure can be a pressure lower than the first pressure. In one example, the first pressure can be greater than 60 Torr and less than 90 Torr, and the second pressure can be greater than 1.5 Torr and less than 20 Torr.

[0106] In another example satisfying condition (B), the processing gas includes carboxylic acid and an inorganic acid such as HBr. In this case, in step ST22-1, the partial pressure of the carboxylic acid can be set to a first pressure, and in step ST22-2, the partial pressure of the carboxylic acid can be set to a second pressure different from the first pressure. The second pressure can be a pressure higher than the first pressure. In one example, the first pressure can be greater than 30 Torr and less than 50 Torr, and the second pressure can be greater than 80 Torr and less than 90 Torr.

[0107] In an example satisfying condition (C), the second temperature may be a temperature lower than the first temperature. In one example, the first temperature may be 110° C. or higher and 130° C. or lower, and the second temperature may be 70° C. or higher and 90° C. or lower.

[0108] 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 is different in the thickness direction, the second region RM2 can be removed with a high selectivity relative to the first region RM1. In addition, the change from the first condition to the second condition can be continuous or staged. In addition, the cycle including the step ST22-1 and the step ST22-2 can be repeated multiple times.

[0109] [Third Embodiment]

[0110] Fig.10 (a) Fig.10 (b) and Fig.10 Each of (c) is a timing diagram showing an example of a substrate processing method according to the third embodiment (hereinafter also referred to as "method MT3"). Method MT3 includes steps ST31 and ST32. In step ST31, a substrate W is provided in the same manner as step ST11 of method MT1. In the next step ST32, the resist film RM is developed. Fig.10 (a) Fig.10 (b) and Fig.10 As shown in (c) of FIG. 1 , the period for performing step ST32 includes a first period and a second period alternating with the first period.

[0111] In one embodiment, the combination of the processing conditions during the first period and the processing conditions during the second period may satisfy any one or more of the following conditions (A) to (C), or may satisfy two or more of them. In addition, in the following description, when the processing gas is a single gas, the pressure of the carboxylic acid refers to the pressure of the carboxylic acid, and when the processing gas is a mixed gas, it refers to the partial pressure of the carboxylic acid.

[0112] (A) In the first period, the resist film RM is developed using the first process gas, and in the second period, the resist film RM is developed using the second process gas different from the first process gas (refer to Fig.10 (a)).

[0113] (B) During the first period, the pressure of the carboxylic acid is set to a first pressure to develop the resist film RM, and during the second period, the pressure of the carboxylic acid is set to a second pressure different from the first pressure to develop the resist film RM (refer to Fig.10 (b)).

[0114] (C) During the first period, the temperature of the substrate support portion 121 is set to a first temperature to develop the resist film RM, and during 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 (refer to Fig.10 (c)).

[0115] In an example satisfying condition (A), a gas containing an inorganic acid may be used as the first process gas, and a gas containing a carboxylic acid may be used as the second process gas. The inorganic acid may be, for example, at least one selected from the group consisting of HBr, BCl3, HCl, and HF. The carboxylic acid may be any one or more of the above-mentioned carboxylic acids.

[0116] In another example satisfying condition (A), a gas containing an organic acid other than carboxylic acid may be used as the first process gas, and a gas containing carboxylic acid may be used as the second process gas. Alternatively, a gas containing carboxylic acid may be used as the first process gas, and a gas containing an organic acid other than carboxylic acid may be used as the second process gas. The gas containing an organic acid other than carboxylic acid may be, for example, the above-mentioned β-dicarbonyl compound or alcohol. The carboxylic acid may be any one or more of the above-mentioned carboxylic acids.

[0117] In another example satisfying condition (A), a gas containing a first carboxylic acid may be used as the first process gas, and a gas containing a second carboxylic acid different from the first carboxylic acid may be used as the second process gas. The first carboxylic acid and the second carboxylic acid may each be any one or more of the above-mentioned carboxylic acids.

[0118] In an example satisfying the condition (B), the first pressure may be greater than or equal to 0 Torr and less than or equal to 0.1 Torr, and the second pressure may be greater than or equal to 1 Torr and less than or equal to 10 Torr.

[0119] In an example satisfying the condition (C), the first temperature may be 110° C. or higher and 130° C. or lower, and the second temperature may be 170° C. or higher and 190° C. or lower.

[0120] According to method MT3, the step of developing (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 can be promoted, and the generation of residues in step ST32 can be suppressed. Fig.10 (b) and Fig.10 In the timing diagram shown in (c), the pressure of the carboxylic acid and the temperature of the substrate support portion 121 are controlled to be "Low" in the first period and "High" in the second period, but can also be controlled to be "High" in the first period and "Low" in the second period.

[0121] [Fourth embodiment]

[0122] Fig.11 1 is a flowchart showing a substrate processing method according to a fourth embodiment (hereinafter also referred to as “method MT4”). Method MT4 includes a step of providing a substrate W (step ST41), a step of removing a portion of the second region (step ST42), a step of forming a deposited film (step ST43), a step of removing slag (step ST44), and a step of removing the second region (step ST45).

[0123] In the MT4 method, as a development processing system, you can use Figure 3 The plasma processing device 1 shown in FIG. 4 can also be used as shown in FIG. Figure 1 The heat treatment apparatus 100 shown in the figure, however, in this case, the processing chamber 102 may be configured to include a plasma supply unit (not shown) capable of supplying plasma generated outside the processing chamber 102 to the processing chamber 102. Figure 3 Method MT4 will be described by taking the case of the plasma processing system shown as an example.

[0124] (Steps ST41 to ST42)

[0125] In step ST41, the substrate W is provided in the same manner as in step ST11. In the next step ST42, a portion of the second region RM2 is removed by developing the resist film RM. In step ST42, the development may be stopped before the base film UF is exposed. A portion of the second region RM2 may be removed by the same process as in the above-mentioned step ST12. The process gas used in step ST42 is the same process gas as that used in step ST11. Fig.12 (a) and Fig.12 Each of (b) is a diagram showing an example of a cross-sectional structure of the substrate W after step ST42. Fig.12 In the example shown in (b), residues (waste residues) S1 to 3 that cannot be completely removed are generated in the process of step ST42. The waste residues S1 to 3 can be removed in step ST44 (waste removal step) described later.

[0126] (Process ST43)

[0127] 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 a plasma generated by a third processing gas containing a carbon-containing gas or a silicon-containing gas. In one example, first, a third processing gas is supplied from a gas supply unit 20 into a plasma processing space 10s. Next, a source RF signal is supplied to an upper electrode or a lower electrode. Thus, a high-frequency electric field is generated in the plasma processing space 10s, and plasma is generated by the third processing gas. Furthermore, free radicals containing carbon or silicon contained in the plasma can be deposited on at least a portion of the resist film RM.

[0128] Fig.13 (a) is a diagram showing an example of a cross-sectional structure of the substrate W after step ST43. Fig.13 As shown in (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 can also be formed on at least a portion of the side surface SS1 of the first region RM1. At this time, the deposited film DF can be formed thicker on the upper surface TS1 than on the side surface SS1 of the first region RM1. Furthermore, the deposited film DF can be further deposited on at least a portion of the upper surface TS2 of the second region RM2. The deposited film DF can 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 wider. Furthermore, 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.

[0129] When forming a carbon-containing film as the deposited film DF, the third process 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 called CH series gas. ), in one example, it can be CH4 gas, C2H2 gas, C2H4 gas or C3H6 gas. The gas can also be fluorocarbon (CxFz: x and z are positive integers. Also called CF series gas.), in one example, it can be C4F6 or C4F8. And the gas can also be hydrofluorocarbon (C x H y F z : x, y and z are positive integers. Also called CHF-based gas. ), in one example, it can be CH2F2 gas or CH3F gas.

[0130] On the other hand, in the case of forming a silicon-containing film as the deposited film DF, the third processing gas may be, for example, a mixed gas of a silicon-containing gas such as SiCl4 gas, 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 deposited film DF may be formed by atomic layer deposition (hereinafter also referred to as "ALD method"). For example, in the case of forming a silicon-containing film as the deposited film DF, the above-mentioned silicon-containing gas may be supplied as a precursor, and after forming 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.

[0131] In one embodiment, as the deposited film DF, a carbon-containing film may be formed after forming the silicon-containing film. In this case, the step ST44 described later may be performed simultaneously with the formation of the carbon-containing film. In one embodiment, as the deposited film DF, a silicon-containing film may be formed after forming the carbon-containing film. In this case, the step ST44 described later may be performed simultaneously with the formation of the silicon-containing film. In addition, in the step ST43, the bias signal (bias RF signal or pulsed first DC signal) may not be supplied to the lower electrode of the substrate support portion 11.

[0132] (Process ST44)

[0133] As described above, when slag is generated in step ST42, a slag removal step (step ST44) may be performed to remove the slag. Fig.12 As shown in (b), the waste residue may include waste residue S1 formed on the side wall of the first region RM1, waste residue S2 extending from the lower part of the exposed part of the first region RM1 toward the surface of the second region RM2, and waste residue S3 formed on the surface of the second region RM2. In step ST44, the waste residues S1 to 3 can be removed by plasma generated by the fourth processing gas. In one example, first, the fourth processing gas is supplied from the gas supply part 20 to the plasma processing space 10s. Then, a source RF signal is supplied to the upper electrode or the lower electrode. Thus, a high-frequency electric field is generated in the plasma processing space 10s, and plasma is generated by the fourth processing gas. At this time, a bias signal can be supplied to the lower electrode of the substrate support part 11. And, the waste residues S1 to 3 are removed by the plasma generated by the fourth processing gas.

[0134] In step ST44, the fourth processing gas may include at least one selected from the group consisting of helium-containing gas, hydrogen-containing gas, bromine-containing gas, and chlorine-containing gas. In one example, the fourth processing gas may include 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 also include a rare gas such as Ar gas or an inert gas such as N2 gas.

[0135] In addition, in step ST44, a part of the deposited film DF may be removed together with the waste residues S1 to 3. For example, a part of the deposited film DF formed on the upper surface TS1 of the first region RM1 may be removed. The deposited film DF can be removed in both the thickness direction and the width direction. Furthermore, in step ST44, a part or all of the remaining part of the second region RM2 may be removed together with the waste residues S1 to 3. That is, step ST44 and step ST45 described later may be performed simultaneously.

[0136] (Process ST45)

[0137] Next, in step ST45, the second region RM2 is further removed. In step ST45, the second region RM2 can be removed by plasma generated by the fifth process gas. In one example, first, the fifth process gas is supplied from the gas supply unit 20 to the plasma processing space 10s. Next, a source RF signal is supplied to the upper electrode or the lower electrode. Thus, a high-frequency electric field is generated in the plasma processing space 10s, and plasma is generated by the fifth process gas. At this time, a bias signal can be supplied to the lower electrode of the substrate support unit 11. In addition, the second region RM2 is removed by free radicals contained in the plasma generated by the fifth process gas.

[0138] In addition, a step of heating the substrate W may be performed after step ST42 and before step ST45. In this case, step ST43 and step ST44 may be omitted. The temperature of the substrate W in the step of heating the substrate W may be above 180°C or above 190°C. The temperature of the substrate W in the step of heating the substrate W may be above 240°C or below 220°C. Furthermore, the step of heating the substrate W and step ST45 may be performed using a single chamber or using two or more different chambers. That is, the chamber used for performing the step of heating the substrate W and the chamber used in step ST45 may be the same chamber, i.e., a single chamber, or may be different chambers.

[0139] Fig.13 (b) is a diagram showing an example of a cross-sectional structure of a substrate W after processing in step ST45. Fig.13As shown in (b), in step ST45, the second region RM2 is removed. In step ST45, the entire deposited film DF formed on the second region RM2 may be removed. In addition, an opening OP defined by the side surface SS1 of the first region RM1 is formed on the base film UF. The upper surface of the base film UF is exposed in the opening OP.

[0140] In step ST45 , the parameters of the plasma treatment for removing the second region RM2 can be appropriately set according to the size (CD: Critical Dimension) of the first region RM1 . This size may be the target size after execution of step ST14 .

[0141] In step ST45, the fifth process gas may be at least one selected from the gases listed as the first process gas, or may be the same gas as the first process gas. The fifth process gas may be at least one selected from the gases listed as the fourth process gas, or may be the same gas as the fourth process gas. Step ST45 may be performed without generating plasma by the heat treatment apparatus 100. At this time, the fifth process gas is supplied into the process chamber 102, the pressure in the process chamber is controlled to a predetermined pressure, and the temperature of the substrate W or the substrate support 121 is adjusted to a predetermined temperature.

[0142] In method MT4, after a portion of the second region RM2 is removed in step ST42, steps ST43, ST44, and ST45 may be performed simultaneously. That is, after the execution of step ST42, the third process gas, the fourth process gas, and the fifth process gas are supplied from the gas supply unit 20 into the plasma processing space 10s. Next, a source RF signal is supplied to the upper electrode or the lower electrode. Thus, a high-frequency electric field is generated in the plasma processing space 10s, and plasma is generated by the third process gas, the fourth process gas, and the fifth process gas. At this time, a bias signal may be supplied to the lower electrode of the substrate support 11. Furthermore, the free radicals generated by the third process gas form a deposited film DF in the first region RM1. On the other hand, the waste residue S1 to 3 and the second region RM2 are removed by the free radicals generated by the fourth process gas and the fifth process gas. That is, the second region RM2 can be removed while the first region RM1 is protected by the deposited film DF. Thus, the size of the first region RM1 can be appropriately controlled while the second region RM2 can be removed.

[0143] Furthermore, in method MT4, after removing the second region RM2 and exposing at least a portion of the base film UF in step ST42, steps ST43, ST44, and ST45 may be performed in sequence, or steps ST43, ST44, and ST45 may be performed simultaneously.

[0144] According to method MT4, after removing at least a portion 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. In addition, in method MT4, the remainder of the second region RM2 or the residue of the second region is removed on the basis of forming the deposited film DF on the first region RM1, so that the surface roughness caused by the unevenness of the side surface SS1 of the first region RM1 and the side surface of the deposited film DF can be reduced.

[0145] [Fifth embodiment]

[0146] Heat treatment systems can replace Figure 1 The heat treatment apparatus 100 shown in FIG. Fig.14 (a) and Fig.14 The heat treatment apparatus 100a shown in (b). Fig.14 (a) is a schematic cross-sectional view showing a configuration example of a heat treatment apparatus 100a. Fig.14 (b) is a schematic top view showing an example of the structure of the heat treatment device 100a. The heat treatment device 100a includes a nozzle 141a and a plurality of gas nozzles 141b on the side wall. The nozzle 141a is disposed at the top of the processing chamber 102. The nozzle 141a can be arranged to be opposite to the substrate support portion 121. The plurality of gas nozzles 141b are disposed on the side wall of the processing chamber 102. The plurality of gas nozzles 141b can be arranged at equal intervals in the circumferential direction along the side wall of the processing chamber 102, for example. The plurality of gas nozzles 141b can include a first gas nozzle 141b1 and a second gas nozzle 141b2. The first gas nozzle 141b1 and the second gas nozzle 141b2 can be arranged alternately in the circumferential direction. The type of gas supplied to the processing chamber 102 from each of the nozzle 141a, the first gas nozzle 141b1 and the second gas nozzle 141b2 can be the same or different. Furthermore, the flow rates of the gases supplied from the shower head 141a, the first gas nozzle 141b1, and the second gas nozzle 141b2 into the processing chamber 102 may be the same or different. In addition, the substrate support 121 and the side wall of the processing chamber 102 may be arranged in the same manner as the heat treatment apparatus 100 (not shown). Furthermore, a gas exhaust port (not shown) may be arranged on the bottom surface side of the processing chamber 102.

[0147] According to the thermal processing apparatus 100a, the gas density in the processing chamber 102 can be easily controlled, and the in-plane uniformity in the development of the resist film RM can be improved.

[0148] [Sixth embodiment]

[0149] As a substrate support, it can replace Figure 1 The substrate support portion 121 shown is used Fig.15The substrate support portion 121a is shown. Fig.15 The substrate support portion 121a shown in the figure 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 along a plane parallel to the substrate W. Fig.15 In the example shown, the substrate support portion 121a has zones Z1 to Z14, and a heater electrode is provided in each zone. The heater electrode in each zone is configured to be able to supply power independently. That is, the substrate support portion 121a is configured to be able to independently control the temperature for each zone. According to the substrate support portion 121a, the in-plane uniformity in the development of the resist film RM can be improved.

[0150] [Seventh embodiment]

[0151] In the substrate processing method of the present invention, the side walls of the processing chamber 102 and / or the parts in the processing chamber 102 (hereinafter also referred to as "parts in the chamber") such as the substrate support portion 121 can be pre-coated before the start of substrate processing (development). The pre-coating can be performed by atomic layer deposition (Atomic Layer Deposition: hereinafter also referred to as "ALD method"), chemical vapor deposition (Chemical Vapor Deposition: hereinafter also referred to as "CVD method"), etc. As a gas for forming a pre-coating layer, a gas that can form a film resistant to a processing gas containing carboxylic acid can be selected. In one example, a silicon-containing gas such as aminosilane or SiCl4 can be used. At this time, a silicon oxide film can be formed as a pre-coating layer on the side walls of the processing chamber 102 and / or the parts in the chamber. Thereby, the corrosion of the side walls of the processing chamber 102 and / or the substrate support portion 121 based on the processing gas can be suppressed.

[0152] In addition, the sidewalls of the processing chamber 102 and / or the components within the chamber may be formed of a material resistant to a processing gas containing carboxylic acid or the like, instead of or in addition to the pre-coat layer.

[0153] Furthermore, in the substrate processing method of the present invention, the processing chamber 102 can be cleaned after the substrate processing (development). At this time, a cleaning gas is supplied to the processing chamber 102 on the basis of heating the processing chamber 102 and the parts in the chamber. As the cleaning gas, for example, a gas containing a hydrogen halide such as HBr or HF can be used. Cleaning can also be performed by a thermal atomic layer etching method (hereinafter also referred to as a "thermal ALE method"). In this way, metal oxides attached to the side walls of the processing chamber 102 and / or the parts in the chamber during development can be removed.

[0154] [Eighth embodiment]

[0155] In the substrate processing method according to the eighth embodiment, the resist film RM developed by any one of the methods MT1 to MT4 is used as a mask to etch the base film UF. The etching conditions of the base film UF can be selected according to the film type of the base film UF. In one embodiment, the etching of the base film UF is performed by Figure 3 The plasma processing device 1 shown is used for execution.

[0156] <Configuration example of substrate processing system>

[0157] Fig.16 This 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 device EX, a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a control unit CT.

[0158] The first carrier station CS1 carries out the loading and unloading of the first carrier C1 between the first carrier station CS1 and the external system of the substrate processing system SS. The first carrier station CS1 has a loading table with a plurality of first loading plates ST1. On each first loading plate ST1, a first carrier C1 in a state of accommodating a plurality of substrates W or in an empty state is loaded. The first carrier C1 has a frame capable of accommodating a plurality of substrates W inside. In one example, the first carrier C1 is a FOUP (Front Opening Unified Pod).

[0159] Furthermore, the first carrier station CS1 transports the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further includes a first transport device HD1. The first transport device HD1 is disposed between the loading table and the first processing station PS1 in the first carrier station CS1. The first transport device HD1 transports and transfers the substrate W between the first carrier C1 on each first loading plate ST1 and the second transport device HD2 of the first processing station PS1. The substrate processing system SS may further include a load lock module. The load lock module may be disposed between the first carrier station CS1 and the first processing station PS1. The load lock module may switch the pressure inside thereof to atmospheric pressure or vacuum. "Atmospheric pressure" may be the pressure inside the first transport device HD1. "Vacuum" refers to a pressure lower than atmospheric pressure, for example, a medium vacuum of 0.1 Pa to 100 Pa. The interior of the second transport device HD2 may be atmospheric pressure or vacuum. The load lock module can, for example, transfer the substrate W from the first transfer device HD1 under atmospheric pressure to the second transfer device HD2 under vacuum, and can transfer the substrate W from the second transfer device HD2 under vacuum to the first transfer device HD1 under atmospheric pressure.

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

[0161] In the pre-processing module PM1, the substrate W is pre-processed. In one embodiment, the pre-processing module PM1 includes a temperature adjustment unit for adjusting the temperature of the substrate W, a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision, etc. In one embodiment, the pre-processing module PM1 includes a surface modification unit for performing surface modification on the substrate W. Each processing unit of the pre-processing module PM1 may include a heat treatment device 100 (see Figure 1 )、Plasma processing device 1 (reference Figure 2 and Figure 3 ) and / or liquid handling equipment.

[0162] In the resist film forming module PM2, a resist film is formed on the substrate W. In one embodiment, the resist film forming module PM2 includes a dry coating unit. The dry coating unit forms the resist film on the substrate W using a dry process such as a vapor deposition method. In one example, the dry coating unit includes a CVD device or an ALD device for chemically vapor depositing a resist film or a PVD device for physically vapor depositing a resist film on the substrate W disposed in the chamber. The dry coating unit may be a thermal treatment device 100 (see Figure 1 ) or plasma processing device 1 (reference Figure 2 and Figure 3 ).

[0163] In one embodiment, the resist film forming module PM2 includes a wet coating unit. The wet coating unit forms a resist film on the substrate W using a wet process such as a solution coating method. In one example, the wet coating unit may be a liquid processing device.

[0164] In one embodiment, examples of the resist film forming module PM2 include both a wet coating unit and a dry coating unit.

[0165] In the first thermal treatment module PM3, the substrate W is thermally treated. In one embodiment, the first thermal treatment module PM3 includes one or more of a pre-baking (PAB) unit for heating the substrate W on which the resist film is formed, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, a plurality of thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see Figure 1 ). Each heat treatment can be performed at a specified temperature using a specified gas.

[0166] The first interface station IS1 includes a third transport device HD3. The third transport device HD3 transports and transfers the substrate W between the first processing station PS1 and the exposure device EX. The third transport device HD3 may include a housing for storing the substrate W, and may control the temperature, humidity, pressure, etc. in the housing.

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

[0168] The second interface station IS2 includes a fourth transport device HD4. The fourth transport device HD4 transports and transfers the substrate W between the exposure device EX and the second processing station PS2. The fourth transport device HD4 may include a housing for storing the substrate W, and may control the temperature, humidity, pressure, etc. in the housing.

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

[0170] In the second thermal treatment module PM4, the substrate W is thermally treated. In one embodiment, the second thermal treatment module PM4 includes one or more of a post-exposure bake (PEB) unit for heating the exposed substrate W, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, a plurality of thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see Figure 1 ). Each heat treatment can be performed at a specified temperature using a specified gas.

[0171] In the measurement module PM5, various measurements are performed on the substrate W. In one embodiment, the measurement module PM5 includes a mounting table for mounting the substrate W, a photographing device, an illumination device, and a photographing unit including various sensors (temperature sensor, reflectivity measurement sensor, etc.). The photographing device may be, for example, a CCD camera for photographing the appearance of the substrate W. Alternatively, the photographing device may be a hyperspectral camera that photographs light by splitting it into wavelengths. The hyperspectral camera can measure one or more of the pattern shape, size, film thickness, composition, and film density of the resist film.

[0172] In the developing module PM6, a developing process is performed on the substrate W. In one embodiment, the developing module PM6 includes a dry developing unit for performing dry developing on the substrate W. The dry developing unit may be, for example, a thermal processing device 100 (see Figure 1 ) or plasma processing device 1 (reference Figure 2 and Figure 3 In one embodiment, the developing module PM6 includes a wet developing unit for wet developing the substrate W. The wet developing unit may be, for example, a liquid processing device. In one embodiment, the developing module PM6 includes both a dry developing unit and a wet developing unit.

[0173] In the third heat treatment module PM7, heat treatment is performed on the substrate W. In one embodiment, the third heat treatment module PM7 includes one or more of a post-bake (PB) unit for heating the developed substrate W, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment devices. In one example, a plurality of heat treatment devices may be stacked. The heat treatment device may be, for example, the heat treatment device 100 (see Figure 1 ). Each heat treatment can be performed at a specified temperature using a specified gas.

[0174] The second carrier station CS2 carries in and carries out the second carrier C2 between the second carrier station CS2 and an external system of the substrate processing system SS. The structure and function of the second carrier station CS2 may be the same as those of the first carrier station CS1 described above.

[0175] The control unit CT controls each structure of the substrate processing system SS to perform a specified process on the substrate W. The control unit CT stores a recipe that sets the process sequence, process conditions, conveying conditions, etc., and controls each structure of the substrate processing system SS in a manner that performs the process assigned to the substrate W according to the recipe. The control unit CT can also be each control unit ( Figure 1 to Figure 3The functions of the control unit 200 and the control unit 2 shown, as well as part or all of the functions of the control unit of the liquid processing device.

[0176] <An example of a substrate processing method>

[0177] Fig.17 1 is a flowchart showing a substrate processing method (hereinafter also referred to as "method MT") according to an exemplary embodiment. Fig.17 As shown, method MT includes a step ST100 of pre-treating a substrate, a step ST200 of forming a resist film on a substrate, a step ST300 of performing a heat treatment (pre-bake: PAB) on the substrate on which the resist film is formed, a step ST400 of performing EUV exposure relative to the substrate, a step ST500 of performing a heat treatment (post-exposure bake: PEB) on the exposed substrate, a step ST600 of measuring the substrate, a step ST700 of developing the resist film on the substrate, a step ST800 of performing a heat treatment (post-bake: PB) on the developed substrate, and a step ST900 of etching the substrate. Method MT may not include one or more of the above-mentioned steps. For example, method MT may not include step ST600, and step ST700 may be performed after step ST500.

[0178] Methods MT can use Fig.16 Hereinafter, a case where the control unit CT of the substrate processing system SS controls each unit of the substrate processing system SS and executes the method MT on the substrate W will be described as an example.

[0179] (Process ST100: Pre-processing)

[0180] First, the first carrier C1 accommodating a plurality of substrates W is moved into the first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on the first loading plate ST1. Then, the substrates W in the first carrier C1 are taken out in sequence by the first conveying device HD1, and are transferred to the second conveying device HD2 of the first processing station PS1. The substrate W is conveyed to the pre-processing module PM1 by the second conveying device HD2. The substrate W is pre-processed by the pre-processing module PM1. The pre-processing may include, for example, one or more of the temperature adjustment of the substrate W, the formation of a part or all of the base film of the substrate W, the heating treatment of the substrate W, and the high-precision temperature adjustment of the substrate W. The pre-processing may include the surface modification treatment of the substrate W.

[0181] (Step ST200: Resist Film Formation)

[0182] Next, the substrate W is transported to the resist film forming module PM2 by the second transport device HD2. A resist film is formed on the substrate W by the resist film forming module PM2. In one embodiment, the formation of the resist film is performed by a wet process such as a liquid phase deposition method. For example, the resist film is spin-coated on the substrate W using a wet coating unit of the resist film forming module PM2, thereby forming the resist film. 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, the resist film is vapor-deposited on the substrate W using a dry coating unit of the resist film forming module PM2, thereby forming the resist film.

[0183] In addition, 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.

[0184] (Process ST300: PAB)

[0185] Next, the substrate W is transported to the first thermal treatment module PM3 by the second transport device HD2. The substrate W is subjected to a heat treatment (pre-baking: PAB) by the first thermal treatment module PM3. The pre-baking may be performed in an air atmosphere or in an inert atmosphere. Furthermore, the pre-baking may be performed by heating the substrate W to a temperature of 50°C to 250°C, 50°C to 200°C, or 80°C to 150°C. In the case where a resist film is formed by a dry process in step ST200, in one embodiment, the pre-baking may be performed continuously in the dry coating unit that performs step ST200. In one embodiment, a process for removing the resist film at the end of the substrate W (edge ​​bead removal: EBR, edge photoresist removal) may be performed after the pre-baking.

[0186] (Process ST400: EUV exposure)

[0187] Next, the substrate W is transferred to the third transport device HD3 of the first interface station IS1 by the second transport device HD2. Furthermore, the substrate W is transported to the exposure device EX by the third transport device HD3. The substrate W is exposed to EUV via an exposure mask (intermediate mask) in the exposure device EX. Thus, a first region where EUV exposure has been completed and a second region where EUV exposure has not been completed are formed on the substrate W in correspondence with the pattern of the exposure mask (intermediate mask).

[0188] (Process ST500: PEB)

[0189] Next, the substrate W is transferred from the fourth conveyor device HD4 of the second interface station IS2 to the fifth conveyor device HD5 of the second processing station PS2. Furthermore, the substrate W is conveyed to the second thermal processing module PM4 by the fifth conveyor device HD5. Furthermore, a heat treatment (post-exposure baking: PEB) is performed on the substrate W in the second thermal processing module PM4. The post-exposure baking can be performed in an air atmosphere. Furthermore, the post-exposure baking can be performed by heating the substrate W to a temperature of 180° C. or higher and 250° C. or lower.

[0190] (Step ST600: Measurement)

[0191] Next, the substrate W is transported to the measuring module PM5 via the fifth transport device HD5. The substrate W is measured by the measuring module PM5. The measurement may be an optical measurement or other measurements. In one embodiment, the measurement based on the measuring module PM5 includes the measurement of the appearance and / or size of the substrate W using a CCD camera. In one embodiment, the measurement based on the measuring module PM5 includes the measurement of one or more of the pattern shape, size, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0192] In one embodiment, the control unit CT determines whether there is an exposure abnormality in the substrate W based on the measured appearance or size and / or pattern shape 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 the development based on the step ST700. The rework of the substrate W can be performed by removing the resist on the substrate W, returning to the step ST200 again and forming a resist film. The rework after the development is sometimes accompanied by damage to the substrate W, but by performing the rework before the development, the damage to the substrate W can be avoided or suppressed.

[0193] (Process ST700: Development)

[0194] Next, the substrate W is transported to the developing module PM6 by the fifth transport device HD5. In the developing module PM6, the resist film on the substrate W is developed. The developing process can be performed by dry developing or wet developing. The developing process can also be performed by combining dry developing and wet developing. The developing process in step ST700 can be performed by the first method (refer to Figure 5 , Fig.11 ) or Method 2 (reference Fig.12 (a) and Fig.12(b)). A desorption process may be performed one or more times after or during the development process. The desorption process includes removing descum or smoothing the surface of the resist film by an inert gas such as helium or a plasma of the inert gas. Furthermore, in the development module PM6, after the development process, the developed resist film may be used as a mask to etch a portion of the base film.

[0195] (Process ST800: PB)

[0196] Next, the substrate W is transported to the third thermal treatment module PM7 by the fifth transport device HD5, and a heating treatment (post-baking) is performed. The post-baking can be performed in an atmospheric atmosphere or in a reduced pressure atmosphere containing N2 or O2. In addition, the post-baking can be performed by heating the substrate W to a temperature above 150°C and below 250°C. In addition to the third thermal treatment module PM7, the post-baking can also be performed in the second thermal treatment module PM4. In one embodiment, the substrate W can be optically measured by the measuring module PM5 after the post-baking. The measurement can be performed on the basis of the measurement in the step ST600, or in place of the measurement in the step ST600. In one embodiment, the control unit CT determines the presence or absence of abnormalities such as defects, damage, adhesion of foreign matter, etc. of the development pattern of the substrate W based on the measured appearance or size and / or pattern shape of the substrate W. In one embodiment, when it is determined that there is an abnormality in the control unit CT, the etching based on the step ST900 can be omitted, and the substrate W can be reworked or discarded. In one embodiment, when it is determined that there is an abnormality in the control unit CT, the opening size of the resist film on the substrate W may be adjusted using a dry coating unit (CVD device, ALD device, etc.).

[0197] (Process ST900: Etching)

[0198] After the execution of step ST800, the substrate W is transferred to the sixth conveying device HD6 of the second carrier station CS2 through the fifth conveying device HD5, and is conveyed to the second carrier C2 of the second mounting plate ST2 through the sixth conveying device HD6. Thereafter, the second carrier C2 is conveyed to a plasma processing system (not shown). In the plasma processing system, the base film UF of the substrate W is etched using the developed resist film as a mask. Thus, the method MT ends. In addition, in step ST700, when the resist film is developed using a plasma processing device, etching can continue to be performed in the plasma processing chamber of the plasma processing device. Furthermore, when the second processing station PS2 is equipped with a plasma processing module in addition to the developing module PM6, etching can also be performed in the plasma processing module. The above-mentioned desorption process can be performed one or more times before or during etching.

[0199] Various exemplary embodiments have been described above, but the present invention is not limited to the exemplary embodiments described above, and various additions, omissions, substitutions, and changes may be made. Furthermore, elements in different embodiments may be combined to form other embodiments.

[0200] The following are various experiments and their results. Fig.18 (a) and Fig.18 (b) Fig.19 (a)~ Fig.19 (d) Figure 20 to Figure 22 , Fig.23 (a)~ Fig.23 (c) Fig.24 (a) and Fig.24 (b) Fig.25 ,as well as Fig.26 . These figures show the results of various experiments. In these figures, "Unexposed" shows the results of an experiment in which an unexposed resist film is developed, and "Exposed" shows the results of an experiment in which an exposed resist film is developed using EUV light. Also, in these figures, "Thickness" shows the thickness of the resist film, and "Normalized Thickness" shows the thickness of the resist film normalized according to the thickness of the resist film in a state before development. In addition, the resist film is a resist film containing tin oxide. Also, in the experiments showing the results in these figures, a resist film was used. Figure 1 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.

[0201] (Experiment 1)

[0202] In Experiment 1, a mixed gas of HBr gas and Ar gas, i.e., a processing gas, was used to develop the unexposed resist film and the exposed resist film. In Experiment 1, the partial pressure of the HBr gas was set to 0.2 Torr (26.6 Pa). In Experiment 1, the temperature of the substrate support during development was set to 10° C. or 20° C.

[0203] Fig.18 (a) shows the results of an experiment in which the temperature of the substrate support portion during development was 10° C., Fig.18 (b) shows the result of the experiment when the temperature of the substrate support portion during development is 60°C. In development, when the temperature of the substrate support portion is 10°C and HBr gas is used, as shown in FIG. Fig.18 As shown in (a), it is confirmed that the residue of the unexposed resist film tends to be easily generated. In addition, when the temperature of the substrate support portion is 60°C and HBr gas is used during development, as shown in Fig.18 As shown in (b), it was confirmed that the unexposed resist film can be removed, but the difference between the reduction rate of the thickness of the unexposed resist film and the reduction rate of the thickness of the exposed resist film can be reduced. In other words, it was confirmed that when HBr gas is used, the unexposed area of ​​the resist film can be removed by setting the temperature of the substrate support portion during development to a high temperature, but the selectivity in development can be reduced.

[0204] (Experiment 2)

[0205] In Experiment 2, the unexposed resist film and the exposed resist film were developed using a processing gas containing only carboxylic acid. In Experiment 2, the pressure of the carboxylic acid, i.e., 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. In Experiment 2, formic acid (H-COOH), trifluoroacetic acid (CF3-COOH), or acetic acid (CH3-COOH) was used as the carboxylic acid.

[0206] Fig.19 (b) Fig.19 (c) and Fig.19 (d) shows the results when formic acid, trifluoroacetic acid, and acetic acid are used as carboxylic acids. Fig.19 (a) indicates that Fig.18 As shown in these figures, it was confirmed that when carboxylic acid is used in development, even if the temperature of the substrate support portion is high, the reduction in the thickness of the exposed resist film can be suppressed, thereby obtaining a high selectivity. In addition, it was confirmed that when formic acid or trifluoroacetic acid is used, a high development speed can be obtained.

[0207] (Experiment 3)

[0208] In Experiment 3, the unexposed resist film and the exposed resist film were developed 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). In Experiment 3, the temperature of the substrate support during development was set to 60°C, 120°C, or 180°C.

[0209] Fig. 20 The results of Experiment 3 are shown. It was confirmed that when formic acid was used, Fig. 20 As shown, development with a high selectivity can be performed at a temperature of 120° C. or higher. Furthermore, it was confirmed that when formic acid was used at a substrate support portion temperature of 180° C., a reduction in the thickness of the exposed resist film was further suppressed compared to when formic acid was used at a substrate support portion temperature of 120° C.

[0210] (Experiment 4)

[0211] In Experiment 4, the unexposed resist film and the exposed resist film were developed 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). In Experiment 4, the temperature of the substrate support during development was set to 60°C, 120°C, or 180°C.

[0212] Fig.21 The results of Experiment 4 are shown. It was confirmed that when trifluoroacetic acid was used, Fig.21 As shown in the figure, it is possible to develop at a high selectivity at a temperature of 120°C or higher. In addition, it was confirmed that when trifluoroacetic acid was used in a state where the temperature of the substrate support portion was 180°C, the reduction in thickness of the exposed resist film was further suppressed compared to the case where trifluoroacetic acid was used in a state where the temperature of the substrate support portion was 120°C. In addition, it was confirmed that when trifluoroacetic acid was used, the reduction in thickness of the exposed resist film was further suppressed compared to the case where formic acid was used.

[0213] (Experiment 5)

[0214] In Experiment 5, the unexposed resist film and the exposed resist film were developed 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). In Experiment 5, the temperature of the substrate support during development was set to 120°C or 180°C.

[0215] Fig. 22 The results of Experiment 5 are shown. It was confirmed that when acetic acid was used, Fig. 22 As shown, development with a high selectivity can be performed at a temperature of 120° C. or higher. In addition, it was confirmed that when acetic acid was used, the reduction in thickness of the resist film after exposure was further suppressed compared to the case of using formic acid or trifluoroacetic acid, but the reduction rate of the thickness of the unexposed resist film was relatively low.

[0216] (Experiment 6)

[0217] In Experiment 6, a mixed gas of trifluoroacetic acid (CF3-COOH) and Ar gas was used as the processing gas, and the unexposed resist film and the exposed resist film were developed. In Experiment 6, the partial pressure of trifluoroacetic acid was set to 3 Torr (400 Pa). In Experiment 6, the temperature of the substrate support during development was set to 90°C, 120°C, or 180°C.

[0218] Fig.23 (a) Fig.23 (b) Fig.23 (c) shows the results when the temperature of the substrate support during development is 90° C., 120° C., and 180° C. As shown in these figures, when trifluoroacetic acid is used, it is confirmed that development can be performed to selectively remove the unexposed area when the substrate support during development is 90° C. or higher.

[0219] (Experiment 7)

[0220] In Experiment 7, a mixed gas of trifluoroacetic acid (CF3-COOH) and Ar gas was used as the processing gas, and the unexposed resist film and the exposed resist film were developed. In Experiment 7, the temperature of the substrate support portion during development was set to 120° C. In Experiment 7, the partial pressure of trifluoroacetic acid was set to 0.36, (48 Pa), 0.6 Torr (80 Pa), 3 Torr (400 Pa), or 6 Torr (798 Pa).

[0221] Fig.24 (a) shows the results related to the development of the unexposed resist film, Fig.24(b) shows the results related to the development of the exposed resist film. As shown in these figures, it was confirmed that when trifluoroacetic acid was used, by setting the partial pressure of trifluoroacetic acid to 0.36 Torr or more, development that selectively removed the unexposed area was possible. In addition, it was confirmed that when trifluoroacetic acid was used, by setting the partial pressure of trifluoroacetic acid to 0.6 Torr or more, development with a high selectivity ratio was possible.

[0222] (Experiment 8)

[0223] In Experiment 8, a mixed gas of acetic acid (CH3-COOH) and Ar gas was used as a processing gas, and the unexposed resist film and the exposed resist film were developed. In Experiment 8, the temperature of the substrate support portion during development was set to 120° C., 150° C., 180° C., or 210° C. In Experiment 8, the partial pressure of acetic acid was set to 0.6 Torr (80 Pa), 3 Torr (400 Pa), or 6 Torr (800 Pa).

[0224] Fig.25 represents the results of Experiment 8. Fig.25 As shown, it was confirmed that when acetic acid was used, by setting the partial pressure of acetic acid to 0.6 Torr or more, development that selectively removed the unexposed area was possible. Also, it was confirmed that when acetic acid was used, by setting the temperature of the substrate support portion to 120° C. or more, development that selectively removed the unexposed area was possible. Also, it was confirmed that when acetic acid was used, by setting the temperature of the substrate support portion to 180° C. or more, the unexposed area could be removed at a high speed, and a high development speed could be obtained.

[0225] (Experiment 9)

[0226] In Experiment 9, a mixed gas of acetic acid (CH3-COOH) and Ar gas was used as a processing gas, and the unexposed resist film and the exposed resist film were developed. In Experiment 9, the temperature of the substrate support portion during development was set to 120° C. or 150° C. In addition, 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).

[0227] Fig.26 Shows the results of Experiment 9. Fig.26As shown, it was confirmed that when acetic acid is used, by setting the partial pressure of acetic acid to a range of 6 Torr to 60 Torr, development that selectively removes the unexposed area can be performed. In addition, it was confirmed that when acetic acid is used, by setting the temperature of the substrate support portion to a temperature of 120° C. or higher, development that selectively removes the unexposed area can be performed. In addition, it was confirmed that when acetic acid is used, if the partial pressure of acetic acid is the same, the higher the temperature of the substrate support portion, the faster the unexposed area can be removed, and a high development speed can be obtained.

[0228] Here, various exemplary embodiments included in the present invention are described in the following [E1] to [E19].

[0229] [E1]

[0230] A substrate processing method comprises the following steps:

[0231] (a) providing a substrate on a substrate support in a processing chamber, wherein in the process, the substrate has a base film and a resist film provided on the base film and formed of a metal-containing resist, the resist film having a first region and a second region; and

[0232] (b) supplying a processing gas containing carboxylic acid into the processing chamber to expose the substrate to the carboxylic acid and selectively removing the second region relative to the first region, thereby dry developing the resist film.

[0233] In the above (b), the pressure or partial pressure of the carboxylic acid is 40Pa or more and less than 13332Pa.

[0234] [E2]

[0235] The substrate processing method according to E1, wherein in (b), the pressure or partial pressure of the carboxylic acid is 133 Pa or more.

[0236] [E3]

[0237] The substrate processing method according to E1, wherein in (b), the pressure or partial pressure of the carboxylic acid is 666 Pa or more.

[0238] [E4]

[0239] The substrate processing method according to E1, wherein in (b), the pressure or partial pressure of the carboxylic acid is 1333 Pa or less.

[0240] [E5]

[0241] The substrate processing method according to E1, wherein the processing gas includes an inert gas, and in (b), the partial pressure of the carboxylic acid is 40 Pa or more.

[0242] [E6]

[0243] According to the substrate processing method described in E5, the partial pressure of the carboxylic acid is 8000 Pa or less.

[0244] [E7]

[0245] The substrate processing method according to any one of E1 to E6, wherein in (b), the temperature of the substrate supporting part is 90° C. or higher.

[0246] [E8]

[0247] The substrate processing method according to any one of E1 to E6, wherein in (b), the temperature of the substrate supporting part is 120° C. or higher.

[0248] [E9]

[0249] The substrate processing method according to any one of E1 to E6, wherein in (b), the temperature of the substrate supporting portion is 300° C. or less.

[0250] [E10]

[0251] 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.

[0252] [E11]

[0253] The substrate processing method according to E8, wherein:

[0254] The carboxylic acid is formic acid,

[0255] In the above (b), the temperature of the substrate supporting part is 120° C. or higher, and the pressure or partial pressure of the carboxylic acid is 40 Pa or higher.

[0256] [E12]

[0257] The substrate processing method according to E8, wherein:

[0258] The carboxylic acid is trifluoroacetic acid,

[0259] In the above (b), the temperature of the substrate supporting part is 90° C. or higher, and the pressure or partial pressure of the carboxylic acid is 40 Pa or higher.

[0260] [E13]

[0261] The substrate processing method according to E8, wherein:

[0262] The carboxylic acid is acetic acid,

[0263] In the above (b), the temperature of the substrate supporting part is 120° C. or higher, and the pressure or partial pressure of the carboxylic acid is 40 Pa or higher.

[0264] [E14]

[0265] The substrate processing method according to any one of E1 to E13, wherein:

[0266] The (b) comprises the following steps:

[0267] (b-1) dry developing the resist film under a first condition; and

[0268] (b-2) dry developing the resist film under a second condition different from the first condition,

[0269] The combination of the first condition and the second condition satisfies at least one of the conditions (A), (B) and (C),

[0270] The condition (A) includes developing the resist using a first process gas in (b-1), and developing the resist film using a second process gas different from the first process gas in (b-2), wherein at least one of the first process gas and the second process gas contains the carboxylic acid,

[0271] The condition (B) includes setting the pressure of the carboxylic acid to a first pressure to develop the resist film in (b-1), and setting the pressure of the carboxylic acid to a second pressure different from the first pressure to develop the resist film in (b-2),

[0272] The condition (C) includes setting the substrate supporting portion to a first temperature to develop the resist film in (b-1), and setting the substrate supporting portion to a second temperature different from the first temperature to develop the resist film in (b-2).

[0273] [E15]

[0274] The substrate processing method according to any one of E1 to E13, wherein:

[0275] The period for performing the above-mentioned (b) includes a first period and a second period alternating with the first period,

[0276] The combination of the processing conditions in the first period and the processing conditions in the second period satisfies at least one of the conditions (A), (B) and (C),

[0277] The condition (A) includes developing the resist film using a first process gas during the first period, and developing the resist film using a second process gas different from the first process gas during the second period, wherein at least one of the first process gas and the second process gas contains the carboxylic acid,

[0278] The condition (B) includes setting the pressure of the carboxylic acid to a first pressure to develop the resist film during the first period, and setting the pressure of the carboxylic acid to a second pressure different from the first pressure to develop the resist film during the second period.

[0279] The condition (C) includes setting the temperature of the substrate support portion to a first temperature to develop the resist film during the first period, and setting the temperature of the substrate support portion to a second temperature different from the first temperature to develop the resist film during the second period.

[0280] [E16]

[0281] The substrate processing method according to any one of E1 to E13, wherein:

[0282] In (b), the second region is partially removed.

[0283] The substrate processing method also includes the following steps:

[0284] After (b), forming a deposited film on the first region;

[0285] removing the residue produced in the step (b) while protecting the first region with the deposited film; and

[0286] The remaining portion of the second region is removed.

[0287] [E17]

[0288] The substrate processing method according to E16, wherein:

[0289] The deposited film is a carbon-containing film or a silicon-containing film,

[0290] The residue is removed by plasma containing at least one processing gas selected from the group consisting of a helium-containing gas, a hydrogen-containing gas, a bromine-containing gas, and a chlorine-containing gas.

[0291] [E18]

[0292] The substrate processing method according to any one of E1 to E13, wherein:

[0293] In (b), the second region is partially removed.

[0294] The substrate processing method also includes the following steps:

[0295] After (b), heating the substrate; and

[0296] The remaining portion of the second region is removed.

[0297] In addition, in the embodiment of E18, the temperature of the substrate in the process of heating the substrate may be 180° C. or more or 190° C. or more. Also, in the embodiment of E18, the temperature of the substrate in the process of heating the substrate may be 240° C. or less or 220° C. or less. Also, in the embodiment of E18, the process of heating the substrate and the process of removing the remaining portion may be performed using a single chamber or two or more different chambers. That is, the chamber used in the process of heating the substrate and the chamber used in the process of removing the remaining portion may be the same chamber, i.e., a single chamber, or may be different chambers.

[0298] [E19]

[0299] A substrate processing system comprising:

[0300] a processing chamber;

[0301] A substrate support portion is disposed in the processing chamber;

[0302] a gas supply unit configured to supply a processing gas containing carboxylic acid into the chamber;

[0303] an exhaust mechanism connected to the processing chamber; and

[0304] Control Department,

[0305] The control unit is configured to control the gas supply unit and the exhaust mechanism in the following manner: in order to dry develop the resist film on the substrate mounted on the substrate support unit, the processing gas is supplied into the chamber to adjust the pressure or partial pressure of the carboxylic acid to be greater than 40 Pa and less than 13332 Pa.

[0306] It can be understood from the above description that various embodiments of the present invention are described in this specification for the purpose of explanation, and various changes can be made without departing from the scope and gist of the present invention. Therefore, the various embodiments disclosed in this specification are not intended to be limiting, and the true scope and gist are represented by the scope of the attached technical solutions.

[0307] Explanation of symbols

[0308] 1-plasma processing device, 2-control unit, 10-plasma processing chamber, 11-substrate support unit, 20-gas supply unit, 30-power supply, 100-heat treatment device, 102-processing chamber, 120-workbench heater, 121-substrate support unit, 141-gas nozzle, 200-control unit, OP-opening, RM-resist film, RM1-first region, RM2-second region, UF-base film, W-substrate.

Claims

1. A substrate processing method, comprising the following steps: (a) providing a substrate on a substrate support in a processing chamber, wherein in the process, the substrate has a base film and a resist film provided on the base film and formed of a metal-containing resist, the resist film having a first region and a second region; and (b) supplying a processing gas containing carboxylic acid into the processing chamber to expose the substrate to the carboxylic acid and selectively removing the second region relative to the first region, thereby dry developing the resist film. In the above (b), the pressure or partial pressure of the carboxylic acid is 40Pa or more and less than 13332Pa.

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

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

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

5. The substrate processing method according to claim 1, wherein: The processing gas includes an inert gas, and in the (b), the partial pressure of the carboxylic acid is 40 Pa or more.

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

7. The substrate processing method according to claim 1, wherein: In the above (b), the temperature of the substrate supporting portion is 90° C. or higher.

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

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

10. The substrate processing method according to claim 1, wherein: The carboxylic acid is at least one selected from the group consisting of formic acid, trifluoroacetic acid, and acetic acid.

11. The substrate processing method according to claim 10, wherein: The carboxylic acid is formic acid, In the above (b), the temperature of the substrate supporting part is 120° C. or higher, and the pressure or partial pressure of the carboxylic acid is 40 Pa or higher.

12. The substrate processing method according to claim 10, wherein: The carboxylic acid is trifluoroacetic acid, In the above (b), the temperature of the substrate supporting part is 90° C. or higher, and the pressure or partial pressure of the carboxylic acid is 40 Pa or higher.

13. The substrate processing method according to claim 10, wherein: The carboxylic acid is acetic acid, In the above (b), the temperature of the substrate supporting part is 120° C. or higher, and the pressure or partial pressure of the carboxylic acid is 40 Pa or higher.

14. The substrate processing method according to any one of claims 1 to 13, wherein: The (b) comprises the following steps: (b-1) dry developing the resist film under a first condition; and (b-2) dry developing the resist film under a second condition different from the first condition, The combination of the first condition and the second condition satisfies at least one of the conditions (A), (B) and (C), The condition (A) includes developing the resist using a first process gas in (b-1), and developing the resist film using a second process gas different from the first process gas in (b-2), wherein at least one of the first process gas and the second process gas contains the carboxylic acid, The condition (B) includes setting the pressure of the carboxylic acid to a first pressure to develop the resist film in (b-1), and setting the pressure of the carboxylic acid to a second pressure different from the first pressure to develop the resist film in (b-2), The condition (C) includes setting the substrate supporting portion to a first temperature to develop the resist film in (b-1), and setting the substrate supporting portion to a second temperature different from the first temperature to develop the resist film in (b-2).

15. The substrate processing method according to any one of claims 1 to 13, wherein: The period for performing the above-mentioned (b) 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 at least one of the conditions (A), (B) and (C), The condition (A) includes developing the resist film using a first process gas during the first period, and developing the resist film using a second process gas different from the first process gas during the second period, wherein at least one of the first process gas and the second process gas contains the carboxylic acid, The condition (B) includes setting the pressure of the carboxylic acid to a first pressure to develop the resist film during the first period, and setting the pressure of the carboxylic acid to a second pressure different from the first pressure to develop the resist film during the second period. The condition (C) includes setting the temperature of the substrate support portion to a first temperature to develop the resist film during the first period, and setting the temperature of the substrate support portion to a second temperature different from the first temperature to develop the resist film during the second period.

16. The substrate processing method according to any one of claims 1 to 13, wherein: In (b), the second region is partially removed. The substrate processing method also includes the following steps: After (b), forming a deposited film on the first region; while protecting the first region with the deposited film, removing the residue generated in the step (b); and The remaining portion of the second region is removed.

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

18. The substrate processing method according to any one of claims 1 to 13, wherein: In (b), the second region is partially removed. The substrate processing method also includes the following steps: After (b), heating the substrate; and The remaining portion of the second region is removed.

19. A substrate processing system comprising: a processing chamber; A substrate support portion is disposed in the processing chamber; a gas supply unit configured to supply a processing gas containing carboxylic acid into the chamber; an exhaust mechanism connected to the processing chamber; and Control Department, The control unit is configured to control the gas supply unit and the exhaust mechanism in the following manner: in order to dry develop the resist film on the substrate mounted on the substrate support unit, the processing gas is supplied into the chamber to adjust the pressure or partial pressure of the carboxylic acid to be greater than 40 Pa and less than 13332 Pa.

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