WO2024024919A1 - 基板処理方法及び基板処理システム - Google Patents

基板処理方法及び基板処理システム Download PDF

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Publication number
WO2024024919A1
WO2024024919A1 PCT/JP2023/027676 JP2023027676W WO2024024919A1 WO 2024024919 A1 WO2024024919 A1 WO 2024024919A1 JP 2023027676 W JP2023027676 W JP 2023027676W WO 2024024919 A1 WO2024024919 A1 WO 2024024919A1
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Prior art keywords
region
substrate
gas
processing method
substrate processing
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PCT/JP2023/027676
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English (en)
French (fr)
Japanese (ja)
Inventor
翔 熊倉
健太 小野
由太 中根
哲也 西塚
昌伸 本田
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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Priority to JP2024537243A priority Critical patent/JP7680814B2/ja
Priority to KR1020257005790A priority patent/KR20250044886A/ko
Priority to EP23846649.4A priority patent/EP4564399A1/en
Priority to CN202380054369.8A priority patent/CN119585842A/zh
Publication of WO2024024919A1 publication Critical patent/WO2024024919A1/ja
Priority to US19/033,671 priority patent/US20250164886A1/en
Anticipated expiration legal-status Critical
Priority to JP2025076917A priority patent/JP2025109743A/ja
Ceased legal-status Critical Current

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    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
    • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/40—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials
    • H10P76/408—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials characterised by their sizes, orientations, dispositions, behaviours or shapes
    • H10P76/4085—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials characterised by their sizes, orientations, dispositions, behaviours or shapes characterised by the processes involved to create the masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/32—Processing objects by plasma generation
    • H01J2237/33—Processing objects by plasma generation characterised by the type of processing
    • H01J2237/332—Coating
    • H01J2237/3321—CVD [Chemical Vapor Deposition]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/32—Processing objects by plasma generation
    • H01J2237/33—Processing objects by plasma generation characterised by the type of processing
    • H01J2237/334—Etching

Definitions

  • Exemplary embodiments of the present disclosure relate to substrate processing methods and substrate processing systems.
  • Patent Document 1 discloses a technique for forming a thin film that can be patterned using extreme ultraviolet light (hereinafter referred to as "EUV") on a semiconductor substrate.
  • EUV extreme ultraviolet light
  • the present disclosure provides a technique for adjusting the shape of a developed pattern.
  • a method of processing a substrate includes: (a) providing a substrate having a base film and a metal-containing resist film on the base film on a substrate support, the step of: the metal-containing resist film includes a first region and a second region; and (b) developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film;
  • the step (b) includes (b1) a step of removing the second region with respect to the first region at a first selection ratio, and (b2) a step of removing the second region with respect to the first region with a first selection ratio. further removing at a second selectivity ratio different from the ratio.
  • a technique for adjusting the shape of a developed pattern can be provided.
  • FIG. 2 is a diagram for explaining a configuration example of a heat treatment system.
  • FIG. 2 is a diagram for explaining a configuration example when a plasma processing system is used as a development processing system.
  • FIG. 2 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.
  • FIG. 2 is a diagram for explaining a configuration example of a liquid processing system.
  • 3 is a flowchart showing a first method. It is a figure which shows an example of the cross-sectional structure of the board
  • 3 is a diagram showing an example of a base film UF of a substrate W.
  • FIG. 3 is a diagram showing an example of a base film UF of a substrate W.
  • FIG. 1 is a diagram showing an example of a base film UF of a substrate W.
  • FIG. 7 is a diagram showing an example of the cross-sectional structure of the substrate W after processing in step ST120.
  • FIG. It is a figure which shows an example of the cross-sectional structure of the board
  • 3 is a flowchart showing a second method.
  • 7 is a diagram showing an example of the cross-sectional structure of the substrate W after processing in step ST220.
  • FIG. 7 is a diagram showing an example of the cross-sectional structure of the substrate W after processing in step ST222.
  • FIG. 1 is a block diagram for explaining a configuration example of a substrate processing system SS.
  • FIG. 3 is a flowchart illustrating method MT.
  • a substrate processing method is provided, including a step of removing the substrate.
  • the first region is the exposed region and the second region is the unexposed region.
  • the second selectivity ratio is higher than the first selectivity ratio.
  • step (b) the development is performed by wet development, and in step (b), the solubility of the metal-containing resist film in the developer used in step (I) (b2) is , the solubility of the metal-containing resist film in the developer used in step (b1) is lower than the solubility of the metal-containing resist film, and (II) the concentration of the developer used in step (b2) is lower than the concentration of the developer used in step (b1). and (III) the temperature of the developer used in step (b2) is lower than the temperature of the developer used in step (b1).
  • step (b) the development is performed by dry development in a chamber, and in step (b), the temperature of the substrate support in step (I) (b2) is ( (II) The pressure inside the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1); (III) (b2) ) The acidity of the second developing gas used in step (b1) is lower than the acidity of the first developing gas used in step (b1), and (IV) the acidity of the second developing gas used in step (b2) is The concentration of the developing gas satisfies at least one of the following conditions: the concentration of the developing gas is lower than the concentration of the first developing gas used in step (b1).
  • (b1) is performed by dry development with a first processing gas that includes a first developer gas
  • (b2) is performed by a second process that includes a second developer gas.
  • the step (b) is carried out by dry development using gas, and the temperature of the substrate support part in the step (I) (b2) is lower than the temperature of the substrate support part in the step (b1); II)
  • the pressure in the chamber in step (b2) is lower than the pressure in the chamber in step (b1), and (III) the acidity of the second developing gas is equal to the acidity of the first developing gas.
  • the concentration of the second developing gas is lower than the concentration of the first developing gas
  • (V) the second processing gas is used in step (b1) and step (b2).
  • the first processing gas contains a protective gas that protects the sidewall of the first region exposed in the process, and the first processing gas does not contain a protective gas or has a lower partial pressure than (the partial pressure of) the protective gas contained in the second processing gas. At least one of the following is satisfied: containing a protective gas at a partial pressure.
  • step (b) the development is performed by dry development using plasma generated in the chamber;
  • the power level of the supplied source RF signal for plasma generation is lower than the power level of the source RF signal in the step (b1), and (II) the power level of the source RF signal supplied to the chamber in the step (b2)
  • the power or voltage level of the bias signal satisfies at least one of the following: the power or voltage level of the bias signal is smaller than the power or voltage level of the bias signal in step (b1).
  • the step (b) further includes a step of modifying the first region between the steps (b1) and (b2).
  • modifying the first region includes heating or plasma treating the substrate.
  • a substrate processing method in which the step of modifying the first region is performed in the same chamber as the step (b1).
  • the step of modifying the first region is performed in a different chamber from the step of (b1).
  • step (b1) development is performed by wet development
  • step (b2) development is performed by dry development.
  • step (b) a cycle including steps (b1) and (b2) is repeated multiple times.
  • the metal-containing resist film includes at least one metal selected from the group consisting of Sn, Hf, and Ti.
  • the first region is exposed to EUV.
  • switching from the step (b1) to the step (b2) is performed based on the depth or aspect ratio of the opening formed in the metal-containing resist film by development.
  • the first region includes a first portion and a second portion below the first portion and on the underlying film, and step (b1) is performed until just before the second portion is exposed. , or until a portion of the second portion is exposed.
  • the method further includes a step of etching the underlying film using the metal-containing resist film as a mask.
  • the method further includes at least one of the steps of removing residues in the first region or the second region generated in (b1) and/or (b2).
  • step (c) is performed in the same chamber used in step (b).
  • step (c) is performed in a different chamber than the chamber used in step (b).
  • the step b) includes (b1) controlling the temperature of the substrate support part to a first temperature and removing the second region, and (b2) controlling the temperature of the substrate support part to be lower than the first temperature.
  • a substrate processing method is provided that includes the step of controlling the temperature to a low second temperature and removing the second region.
  • the step (b) is dry developing using HBr, the first temperature is 20°C or more and 60°C or less, and the second temperature is -20°C. The temperature is above 20°C.
  • a method of processing a substrate includes: (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support; (b) dry developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film; The step (b) includes (b1) removing the second region using the first processing gas, and (b2) using the second processing gas having a lower acidity than the first processing gas.
  • a method for processing a substrate is provided, including the step of removing the second region using a processing gas of:
  • the first processing gas includes a halogen-containing inorganic acid and the second processing gas includes an organic acid.
  • the first process gas includes a halogen-containing inorganic acid and an organic acid at a lower flow rate than the halogen-containing inorganic acid
  • the second process gas includes a halogen-containing inorganic acid and a lower flow rate of the organic acid than the halogen-containing inorganic acid.
  • the organic acid contains a higher flow rate than the inorganic acid contained therein.
  • the halogen-containing inorganic acid includes at least one selected from the group consisting of HBr gas, HCl gas, BCl3 gas, and HF gas and HI gas.
  • the organic acid includes at least one selected from the group consisting of carboxylic acids, ⁇ -dicarbonyl compounds, and alcohols.
  • step (b) comprises (I) the temperature of the substrate support in step (b2) is lower than the temperature of the substrate support in step (b1); and (II). )
  • the pressure in the chamber in the step (b2) satisfies at least one of the following conditions: the pressure in the chamber in the step (b1) is lower than the pressure in the chamber in the step (b1).
  • steps (b1) and (b2) are repeated.
  • step (b) a cycle including steps (b1) and (b2) is performed one or more times, and then step (b1) is further performed.
  • step (b) is performed after the cycle including steps (b1) and (b2) is performed one or more times without using a plasma. and/or removing the second region using plasma generated from the second processing gas.
  • a substrate processing system having one or more substrate processing apparatuses and a controller, wherein the controller controls (a) a base film and a base film for the one or more substrate processing apparatuses; (b) providing a substrate having a metal-containing resist film on a substrate support on a substrate support, the metal-containing resist film including a first region and a second region; and selectively removing the second region from the metal-containing resist film by developing the resist film, and the control in (b) includes: (b1) developing the second region with respect to the first region; A substrate processing system includes: (b2) control to remove a second region with respect to the first region at a second selection ratio different from the first selection ratio; provided.
  • FIG. 1 is a diagram for explaining a configuration example of a heat treatment system.
  • the heat treatment system includes a heat treatment apparatus 100 and a controller 200.
  • the heat processing system is an example of a substrate processing system
  • the heat processing apparatus 100 is an example of a substrate processing apparatus.
  • the heat treatment apparatus 100 includes a treatment chamber 102 configured to form a sealed space.
  • the processing chamber 102 is, for example, an airtight cylindrical container, and is configured to be able to adjust the internal atmosphere.
  • a side wall heater 104 is provided on the side wall of the processing chamber 102 .
  • a ceiling heater 130 is provided on the ceiling wall (top plate) of the processing chamber 102 .
  • a ceiling surface 140 of the ceiling wall (top plate) of the processing chamber 102 is formed as a horizontal flat surface, and its temperature is adjusted by the ceiling heater 130.
  • a substrate support section 121 is provided on the lower side inside the processing chamber 102.
  • the substrate support section 121 has a substrate support surface on which the substrate W is supported.
  • the substrate support part 121 is, for example, formed in a circular shape in plan view, and the substrate W is placed on the horizontally formed surface (upper surface) thereof.
  • a stage heater 120 is embedded in the substrate support section 121. This stage heater 120 can heat the substrate W placed on the substrate support section 121.
  • a ring assembly (not shown) may be arranged in the substrate support section 121 so as to surround the substrate W.
  • the ring assembly may include one or more annular members. By arranging the ring assembly around the substrate W, temperature controllability in the outer peripheral region of the substrate W can be improved.
  • the ring assembly may be constructed from inorganic or organic materials depending on the intended heat treatment.
  • the substrate support part 121 is supported within the processing chamber 102 by a support 122 provided on the bottom surface of the processing chamber 102.
  • a plurality of lifting pins 123 that can be vertically moved up and down are provided on the outer side of the support column 122 in the circumferential direction.
  • Each of the plurality of lifting pins 123 is inserted into a through hole provided in the substrate support section 121.
  • the plurality of lifting pins 123 are arranged at intervals in the circumferential direction.
  • the elevating and lowering operations of the plurality of elevating pins 123 are controlled by an elevating mechanism 124.
  • An exhaust port 131 having an opening is provided in the side wall of the processing chamber 102.
  • the exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe.
  • the exhaust mechanism 132 is composed of a vacuum pump, a valve, and the like, and adjusts the exhaust flow rate from the exhaust port 131. By adjusting the exhaust flow rate and the like by the exhaust mechanism 132, the pressure inside the processing chamber 102 is adjusted.
  • a transport port for the substrate W (not shown) is formed in the side wall of the processing chamber 102 at a position different from the position where the exhaust port 131 opens so as to be openable and closable.
  • 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 substrate W transport port. Gas nozzle 141 supplies processing gas into processing chamber 102 .
  • the gas nozzle 141 is provided on the side wall of the processing chamber 102 on the opposite side of the exhaust port 131 when viewed from the center of the substrate support 121 . That is, the gas nozzle 141 is provided on the side wall of the processing chamber 102 symmetrically with the exhaust port 131 with respect to a vertical imaginary plane passing through the center of the substrate support 121 .
  • the gas nozzle 141 is formed into a rod shape that protrudes from the side wall of the processing chamber 102 toward the center of the processing chamber 102 .
  • the tip of the gas nozzle 141 extends, for example, horizontally from the side wall of the processing chamber 102.
  • the processing gas is discharged into the processing chamber 102 from a discharge port that opens at the tip of the gas nozzle 141, flows in the direction of the dashed-dotted arrow shown in FIG. 1, and is exhausted from the exhaust port 131.
  • the tip of the gas nozzle 41 may have a shape extending diagonally downward toward the substrate W, or may have a shape extending diagonally upward toward the ceiling surface 140 of the processing chamber 102.
  • gas nozzle 141 may be provided, for example, on the ceiling wall of the processing chamber 102. Further, the exhaust port 131 may be provided on the bottom surface of the processing chamber 102.
  • the heat treatment apparatus 100 has a gas supply pipe 152 connected to the gas nozzle 141 from the outside of the treatment chamber 102.
  • a pipe heater 160 is provided around the gas supply pipe 152 to heat the gas within the gas supply pipe 152 .
  • Gas supply pipe 152 is connected to gas supply section 170.
  • Gas supply 170 includes at least one gas source and at least one flow controller.
  • the gas supply may include a vaporizer that vaporizes the material in liquid form.
  • the control unit 200 processes computer-executable instructions that cause the heat treatment apparatus 100 to perform various steps described in this disclosure.
  • Control unit 200 may be configured to control each element of heat treatment apparatus 100 to perform the various steps described herein. In one embodiment, part or all of the control unit 200 may be included in the heat treatment apparatus 100.
  • the control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3.
  • the control unit 200 is realized by, for example, a computer 200a.
  • the processing unit 200a1 may be configured to read a program from the storage unit 200a2 and perform various control operations by executing the read program. This program may be stored in advance in the storage unit 200a2, or may be acquired via a medium when necessary.
  • the acquired program is stored in the storage unit 200a2, and is read out from the storage unit 200a2 and executed by the processing unit 200a1.
  • the medium may be any of various storage media readable by the computer 200a, or may be a communication line connected to the communication interface 200a3.
  • the processing unit 200a1 may be a CPU (Central Processing Unit).
  • the storage unit 200a2 may include a RAM (Random Access Memory), a ROM (Read Only Memory), an HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof.
  • the communication interface 200a3 may communicate with the heat treatment apparatus 100 via a communication line such as a LAN (Local Area Network).
  • FIG. 2 is a diagram for explaining a configuration example when a plasma processing system is used as a development processing system.
  • a plasma processing system includes a plasma processing apparatus 1 and a controller 2.
  • the plasma processing system is an example of a substrate processing system
  • the plasma processing apparatus 1 is an example of a substrate processing apparatus.
  • the plasma processing apparatus 1 includes a plasma processing chamber (hereinafter also simply referred to as a "processing chamber") 10, a substrate support section 11, and a plasma generation section 12.
  • the plasma processing chamber 10 has a plasma processing space.
  • the plasma processing chamber 10 also includes 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 discharging gas from the plasma processing space.
  • the gas supply port is connected to a gas supply section 20, which will be described later, and the gas discharge port is connected to an exhaust system 40, which will be described later.
  • the substrate support section 11 is disposed within the plasma processing space and has a substrate support surface for supporting a substrate.
  • the plasma generation unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space.
  • the plasmas formed in the plasma processing space are capacitively coupled plasma (CCP), inductively coupled plasma (ICP), and ECR plasma (Electron-Cyclotron-resonance plasma).
  • CCP capacitively coupled plasma
  • ICP inductively coupled plasma
  • ECR plasma Electro-Cyclotron-resonance plasma
  • HWP Helicon wave excited plasma
  • SWP surface wave plasma
  • various types of plasma generation sections may be used, including an AC (Alternating Current) plasma generation section and a DC (Direct Current) plasma generation section.
  • the AC signal (AC power) used in the AC plasma generator has a frequency in the range of 100 kHz to 10 GHz. Therefore, the AC signal includes an RF (Radio Frequency) signal and a microwave signal.
  • the RF signal has a frequency within the range of 100kHz to 150MHz.
  • the control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform various steps described in this disclosure.
  • the control unit 2 may be configured to control each element of the plasma processing apparatus 1 to perform the various steps described herein. In one embodiment, part or all of the control unit 2 may be included in the plasma processing apparatus 1.
  • the control unit 2 is realized by, for example, a computer 2a.
  • the control unit 2 may include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. Each configuration of the control unit 2 may be similar to each configuration of the control unit 200 (see FIG. 1) described above.
  • FIG. 3 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.
  • the capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply section 20, a power supply 30, and an exhaust system 40. Further, the plasma processing apparatus 1 includes a substrate support section 11 and a gas introduction section. The gas inlet is configured to introduce at least one processing gas into the plasma processing chamber 10 .
  • the gas introduction section includes a shower head 13.
  • Substrate support 11 is arranged within plasma processing chamber 10 .
  • the shower head 13 is arranged above the substrate support section 11 . In one embodiment, showerhead 13 forms at least a portion of the ceiling of plasma processing chamber 10 .
  • the plasma processing chamber 10 has a plasma processing space 10s defined by a shower head 13, a side wall 10a of the plasma processing chamber 10, and a substrate support 11. Plasma processing chamber 10 is grounded.
  • the shower head 13 and the substrate support section 11 are electrically insulated from the casing of the plasma processing chamber 10.
  • the substrate support section 11 includes a main body section 111 and a ring assembly 112.
  • the main body portion 111 has a central region 111a for supporting the substrate W and an annular region 111b for supporting the ring assembly 112.
  • a wafer is an example of a substrate W.
  • the annular region 111b of the main body 111 surrounds the central region 111a of the main body 111 in plan view.
  • the substrate W is placed on the central region 111a of the main body 111, and the ring assembly 112 is placed on the annular region 111b of the main body 111 so as to surround the substrate W on the central region 111a of the main body 111. Therefore, the central region 111a is also called a substrate support surface for supporting the substrate W, and the annular region 111b is also called a ring support surface for supporting the ring assembly 112.
  • the main body 111 includes a base 1110 and an electrostatic chuck 1111.
  • Base 1110 includes a conductive member.
  • the conductive member of the base 1110 can function as a lower electrode.
  • Electrostatic chuck 1111 is placed on base 1110.
  • Electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within ceramic member 1111a.
  • Ceramic member 1111a has a central region 111a. In one embodiment, ceramic member 1111a also has an annular region 111b. Note that another member surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member, may have the annular region 111b.
  • ring assembly 112 may be placed on the annular electrostatic chuck or the annular insulation member, or may be placed on both the electrostatic chuck 1111 and the annular insulation member.
  • at least one RF/DC electrode coupled to an RF power source 31 and/or a DC power source 32, which will be described later, may be disposed within the ceramic member 1111a.
  • at least one RF/DC electrode functions as a bottom electrode.
  • An RF/DC electrode is also referred to as a bias electrode if a bias RF signal and/or a DC signal, as described below, is supplied to at least one RF/DC electrode.
  • the conductive member of the base 1110 and at least one RF/DC electrode may function as a plurality of lower electrodes.
  • the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support 11 includes at least one lower electrode.
  • Ring assembly 112 includes one or more annular members.
  • the one or more annular members include one or more edge rings and at least one cover ring.
  • the edge ring is made of a conductive or insulating material
  • the cover ring is made of an insulating material.
  • the substrate support unit 11 may include a temperature control module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature.
  • the temperature control module may include a heater, a heat transfer medium, a flow path 1110a, or a combination thereof.
  • a heat transfer fluid such as brine or gas flows through the flow path 1110a.
  • a channel 1110a is formed within the base 1110 and one or more heaters are disposed within the ceramic member 1111a of the electrostatic chuck 1111.
  • the substrate support section 11 may include a heat transfer gas supply section configured to supply heat transfer gas to the gap between the back surface of the substrate W and the central region 111a.
  • the shower head 13 is configured to introduce at least one processing gas from the gas supply section 20 into the plasma processing space 10s.
  • the shower head 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and a plurality of gas introduction ports 13c.
  • the processing gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the plurality of gas introduction ports 13c.
  • the showerhead 13 also includes at least one upper electrode.
  • the gas introduction section may include one or more side gas injectors (SGI) attached to one or more openings formed in the side wall 10a.
  • SGI side gas injectors
  • the gas supply section 20 may include at least one gas source 21 and at least one flow rate controller 22.
  • the gas supply 20 is configured to supply at least one process gas from a respective gas source 21 to the showerhead 13 via a respective flow controller 22 .
  • Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller.
  • gas supply 20 may include at least one flow modulation device that modulates or pulses the flow rate of at least one process gas.
  • Power supply 30 includes an RF power supply 31 coupled to plasma processing chamber 10 via at least one impedance matching circuit.
  • RF power source 31 is configured to supply at least one RF signal (RF power) to at least one bottom electrode and/or at least one top electrode.
  • RF power supply 31 can function as at least a part of the plasma generation section 12. Further, by supplying a bias RF signal to at least one lower electrode, a bias potential is generated in the substrate W, and ion components in the formed plasma can be drawn into the substrate W.
  • the RF power supply 31 includes a first RF generation section 31a and a second RF generation section 31b.
  • the first RF generation section 31a is coupled to at least one lower electrode and/or at least one upper electrode via at least one impedance matching circuit, and generates a source RF signal (source RF power) for plasma generation. It is configured as follows.
  • the source RF signal has a frequency within the range of 10 MHz to 150 MHz.
  • the first RF generator 31a may be configured to generate multiple source RF signals having different frequencies. The generated one or more source RF signals are provided to at least one bottom electrode and/or at least one top electrode.
  • the second RF generating section 31b is coupled to at least one lower electrode via at least one impedance matching circuit, and is configured to generate a bias RF signal (bias RF power).
  • the frequency of the bias RF signal may be the same or different than the frequency of the source RF signal.
  • the bias RF signal has a lower frequency than the frequency of the source RF signal.
  • the bias RF signal has a frequency within the range of 100kHz to 60MHz.
  • the second RF generator 31b may be configured to generate multiple bias RF signals having different frequencies.
  • the generated one or more bias RF signals are provided to at least one bottom electrode. Also, in various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.
  • Power source 30 may also include a DC power source 32 coupled to plasma processing chamber 10 .
  • the DC power supply 32 includes a first DC generation section 32a and a second DC generation section 32b.
  • the first DC generator 32a is connected to at least one lower electrode and configured to generate a first DC signal.
  • the generated first DC signal is applied to at least one bottom electrode.
  • the second DC generator 32b is connected to the at least one upper electrode and configured to generate a second DC signal.
  • the generated second DC signal is applied to the at least one top electrode.
  • the first and second DC signals may be pulsed.
  • 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 that is rectangular, trapezoidal, triangular, or a combination thereof.
  • a waveform generator for generating a sequence of voltage pulses from a DC signal is connected between the first DC generator 32a and the at least one bottom electrode. Therefore, the first DC generation section 32a and the waveform generation section constitute a voltage pulse generation section.
  • the voltage pulse generation section is connected to at least one upper electrode.
  • the voltage pulse may have positive polarity or negative polarity.
  • the sequence of voltage pulses may include one or more positive voltage pulses and one or more negative voltage pulses within one cycle.
  • the first and second DC generation units 32a and 32b may be provided in addition to the RF power source 31, or the first DC generation unit 32a may be provided in place of the second RF generation unit 31b. good.
  • the exhaust system 40 may be connected to a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10, for example.
  • Evacuation system 40 may include a pressure regulating valve and a vacuum pump. The pressure within the plasma processing space 10s is adjusted by the pressure regulating valve.
  • the vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.
  • FIG. 4 is a diagram for explaining a configuration example of a liquid processing system.
  • the liquid processing system includes a liquid processing device 300 and a control unit 400.
  • the liquid processing system is an example of a substrate processing system
  • the liquid processing apparatus 300 is an example of a substrate processing apparatus.
  • the liquid processing apparatus 300 has a spin chuck 311 as a substrate support part in a processing chamber 310.
  • the spin chuck 311 holds the substrate W horizontally.
  • the spin chuck 311 is connected to a rotating part 312 that can be raised and lowered, and the rotating part 312 is connected to a rotational drive part 313 formed by a motor or the like.
  • the substrate W held by the spin chuck 311 can be rotated by driving the rotation drive unit 313 .
  • a cup 321 is placed outside the spin chuck 311 to prevent processing liquid (resist liquid, developer, cleaning liquid, etc.) and processing liquid mist from scattering around the cup 321.
  • a drain pipe 323 and an exhaust pipe 324 are provided at the bottom 322 of the cup 321 .
  • the drain pipe 323 leads to a drain device 325, such as a drain pump.
  • the exhaust pipe 324 communicates via a valve 326 with an exhaust device 327 such as an exhaust pump.
  • a blower device 314 is provided above the processing chamber 310 of the liquid processing device 300 to supply air at the required temperature and humidity into the cup 321 as a downflow.
  • the processing liquid supply nozzle 331 When forming a puddle of processing liquid on the substrate W, the processing liquid supply nozzle 331 is used.
  • the processing liquid supply nozzle 331 is provided on a nozzle support part 332 such as an arm, and the nozzle support part 332 can be raised and lowered by a drive mechanism as shown by the reciprocating arrow A shown by the broken line in the figure. It is horizontally movable as shown by the reciprocating arrow B indicated by a broken line.
  • a processing liquid resist solution, developer, etc.
  • a processing liquid is supplied to the processing liquid supply nozzle 331 from a processing liquid supply source 334 via a supply pipe 333 .
  • forming a puddle of the processing liquid can be done by scanning the substrate W with a straight type nozzle in the same way as a long nozzle, or by lining up multiple discharge ports for discharging liquid on the substrate W like a straight type nozzle, and arranging each discharge port individually.
  • the treatment liquid may be supplied from the source.
  • the gas nozzle 341 has a nozzle body 342.
  • the nozzle main body 342 is provided on a nozzle support part such as an arm, and the nozzle support part can be moved up and down by a drive mechanism as shown by the reciprocating arrow C shown by the broken line in the figure. It is horizontally movable as shown by arrow D.
  • the gas nozzle 341 has two nozzle discharge ports 343 and 344.
  • the nozzle discharge ports 343 and 344 are formed to branch from the gas flow path 345.
  • the gas flow path 345 communicates with a gas supply source 347 via a gas supply pipe 346.
  • the gas supply source 347 is prepared with nitrogen gas, for example, as an inert gas or non-oxidizing gas. When nitrogen gas, for example, is supplied to the gas nozzle 341 from the gas flow path 345, the nitrogen gas is discharged from each nozzle discharge port 343, 344.
  • the gas nozzle 341 is provided with a cleaning liquid supply nozzle 351 that cleans the processing liquid from the substrate W after liquid processing.
  • the cleaning liquid supply nozzle 351 communicates with a cleaning liquid supply source 353 via a cleaning liquid supply pipe 352 .
  • a cleaning liquid supply pipe 352 For example, pure water is used as the cleaning liquid.
  • the cleaning liquid supply nozzle 351 is located between the two nozzle discharge ports 343 and 344 described above, its position is not limited to this.
  • the cleaning liquid supply nozzle 351 may be configured independently from the gas nozzle 341.
  • the control unit 400 processes computer-executable instructions that cause the liquid processing device 300 to perform various steps described in this disclosure.
  • Control unit 400 may be configured to control each element of liquid processing apparatus 300 to perform the various steps described herein. In one embodiment, part or all of the control unit 400 may be included in the liquid processing device 300.
  • the control unit 400 is realized by, for example, a computer 400a.
  • the computer 400a may include a processing section 400a1, a storage section 400a2, and a communication interface 400a3.
  • Each configuration of the control unit 400 may be similar to each configuration of the control unit 200 (see FIG. 1) described above.
  • FIG. 5 is a flowchart showing a substrate processing method (hereinafter also referred to as "first method") according to the first exemplary embodiment.
  • the first method includes a step ST11 of providing a substrate and a step ST12 of developing the substrate.
  • the development process in step ST12 is performed by a dry process (hereinafter also referred to as "dry development") using a processing gas.
  • the development process in step ST12 is performed by a wet process using a developer (hereinafter also referred to as "wet development”).
  • the development process in step ST12 is performed using both wet development and dry development.
  • the first method may be performed using any one of the substrate processing systems described above (see FIGS. 1 to 4), or may be performed using two or more of these substrate processing systems. .
  • the first method may be performed in a heat treatment system (see FIG. 1).
  • FIG. 1 a case where the control section 200 controls each section of the heat treatment apparatus 100 to execute the first method on the substrate W will be described as an example.
  • step ST11 the substrate W is provided in the processing chamber 102 of the heat processing apparatus 100.
  • the substrate W is provided on the substrate support part 121 via the lifting pins 123.
  • the temperature of the substrate support 121 is adjusted to a set temperature.
  • the temperature of the substrate support part 121 can be adjusted by controlling the output of one or more heaters among the side wall heater 104, the stage heater 120, the ceiling heater 130, and the pipe heater 160 (hereinafter also referred to as "each heater"). You can do it.
  • the temperature of the substrate support part 121 may be adjusted to a set temperature before step ST11. That is, the substrate W may be provided on the substrate support 121 after the temperature of the substrate support 121 is adjusted to the set temperature.
  • FIG. 6 is a diagram showing an example of the cross-sectional structure of the substrate W provided in step ST11.
  • the substrate W includes a base film UF and a resist film RM formed on the base film UF.
  • the substrate W may be used for manufacturing semiconductor devices.
  • Semiconductor devices include, for example, memory devices such as DRAMs and 3D-NAND flash memories, and logic devices.
  • the resist film RM is a metal-containing resist film containing metal.
  • the metal may include at least one metal selected from the group consisting of Sn, Hf, and Ti.
  • the resist film RM contains Sn, and may include tin oxide (SnO) and tin hydroxide (Sn—OH bond).
  • the resist film RM may further contain an organic substance.
  • the resist film RM has an exposed first region RM1 and an unexposed second region RM2.
  • the first region RM1 is a region exposed to EUV light, that is, an EUV exposure region.
  • the second region RM2 is a region not exposed to EUV light, that is, an unexposed region.
  • the thickness of the first region RM1 may be smaller than the thickness of the second region RM2.
  • the base film UF may be an organic film, a dielectric film, a metal film, a semiconductor film, or a laminated film of these formed on a silicon wafer.
  • the base film UF includes, for example, at least one selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film.
  • the base film UF may be composed of a first film UF1, a second film UF2, and a third film UF3.
  • the base film UF may be composed of a second film UF2 and a third film UF3.
  • the first film UF1 is, for example, a spin-on-glass (SOG) film, a SiC film, a SiON film, a Si-containing antireflection film (SiARC), or an organic film.
  • the second film UF2 is, for example, a spin-on carbon (SOC) film, an amorphous carbon film, or a silicon-containing film.
  • the third film UF3 is, for example, a silicon-containing film.
  • the silicon-containing film is, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbonitride film, a polycrystalline silicon film, or a carbon-containing silicon film.
  • the third film UF3 may be composed of a plurality of stacked silicon-containing films.
  • the third film UF3 may be composed of a silicon oxide film and a silicon nitride film that are alternately stacked.
  • the third film UF3 may be composed of a silicon oxide film and a polycrystalline silicon film that are alternately stacked.
  • the third film UF3 may be a laminated film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film.
  • the third film UF3 may be composed of a stacked silicon oxide film and silicon carbonitride film.
  • the third film UF3 may be a laminated film including a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.
  • the substrate W is formed as follows. First, a metal-containing photoresist film is formed on a base film that has been subjected to adhesion treatment and the like. Film formation may be performed by a dry process, a wet process such as a solution coating method, or both a dry process and a wet process. Note that the base film may be subjected to surface modification treatment before the photoresist film is formed. After the photoresist film has been formed on the substrate, the substrate is subjected to a heat treatment, that is, a pre-bake (Post Apply Bake: PAB). The substrate after prebaking may be subjected to additional heat treatment.
  • a pre-bake Post Apply Bake: PAB
  • the wafer after the heat treatment is transferred to an exposure device, and the photoresist film is irradiated with EUV light through an exposure mask (reticle).
  • a substrate W including the base film UF and the resist film RM having the exposed first region RM1 and the unexposed second region RM2 is formed.
  • the first region RM1 is a region corresponding to an opening provided in an exposure mask (reticle).
  • the second region RM2 is a region corresponding to a pattern provided on an exposure mask (reticle).
  • EUV light has a wavelength in the range of 10-20 nm, for example. EUV light may have a wavelength in the range of 11-14 nm, in one example having a wavelength of 13.5 nm.
  • the exposed substrate is transported from the exposure apparatus to the heat treatment apparatus under controlled atmosphere, and undergoes heat treatment, that is, post exposure bake (PEB).
  • the substrate W after PEB may be subjected to additional heat treatment.
  • the exposure reaction is weak along the thickness direction of the resist film RM (the direction of arrow D in FIGS. 6 to 8, hereinafter also referred to as the "depth direction"). There may be some parts. This is thought to be due to stochastic fluctuations in the photon distribution of EUV and the shallow depth of focus.
  • the first region RM1 includes a first portion RM1a and a second portion RM1b having a weaker exposure reaction than the first portion RM1a along the thickness direction.
  • the second portion RM1b is a portion in contact with the base layer UF in the first region RM1.
  • the second portion RM1b Since the second portion RM1b has a weak exposure reaction, its film properties are similar to those of the second region RM2, which is an unexposed region. Therefore, in the resist film RM shown in FIGS. 6 to 8, it becomes difficult to maintain the development contrast (ratio of development speed between the exposed area and the unexposed area) along the thickness direction.
  • the side surface below the first region RM1 (second portion RM1b) becomes easier to be removed together with the second region RM2.
  • FIG. 9 is a diagram showing an example of the cross-sectional structure of the substrate W after development.
  • FIG. 9 is an example of the case where the substrate W shown in FIG. 6 is developed under the same conditions along the thickness direction.
  • the cross-sectional dimension of the second portion RM1b becomes smaller along the thickness direction, and has an inversely tapered shape. This is thought to be because the second portion RM1b of the first region RM1 has a smaller development contrast with respect to the second region RM2 along the thickness direction than the first portion RM1a, and is likely to be removed by development together with the second region RM2. It will be done. Therefore, in the first method, step ST121 and step ST122 are developed under different conditions.
  • step ST121 and step ST122 development is performed with different development contrasts in step ST121 and step ST122.
  • Step ST12 Development of substrate
  • step ST12 the resist film RM on the substrate W is developed, and the second region RM2 is selectively removed.
  • Step ST12 includes a step ST120 of developing the substrate with a first selectivity ratio, and a step ST122 of developing the substrate with a second selectivity ratio different from the first selectivity ratio.
  • a first processing gas containing a first developing gas is supplied into the processing chamber 102 via the gas nozzle 141.
  • the first development gas includes a halogen-containing gas.
  • the halogen-containing gas may be a gas containing a halogen-containing inorganic acid, or may be a gas containing Br or Cl.
  • the gas containing the halogen-containing inorganic acid may be a gas containing hydrogen halide and/or boron halide.
  • the gas containing the halogen-containing inorganic acid is at least one selected from the group consisting of HBr gas, BCl 3 gas, HCl gas, and HF gas and HI gas.
  • the first developing gas may be a gas containing an organic acid.
  • the gas containing an organic acid may be, for example, a gas containing at least one selected from the group consisting of carboxylic acids, ⁇ -dicarbonyl compounds, and alcohols.
  • the first developing gas is a gas containing a carboxylic acid.
  • Carboxylic acids include, for example, formic acid (HCOOH), acetic acid ( CH3COOH ), trichloroacetic acid (CCl3COOH ), monofluoroacetic acid ( CFH2COOH ), difluoroacetic acid (CF2FCOOH), trifluoroacetic acid ( CF3COOH ).
  • Chloro-difluoroacetic acid (CClF 2 COOH) sulfur-containing acetic acid, thioacetic acid (CH 3 COSH), thioglycolic acid (HSCH 2 COOH), trifluoroacetic anhydride ((CF 3 CO) 2 O), acetic anhydride ( (CH 3 CO) 2 O) may be used.
  • the first development gas includes a ⁇ -dicarbonyl compound.
  • ⁇ -dicarbonyl compounds include acetylacetone (CH 3 C(O)CH 2 C(O)CH 3 ), trichloroacetylacetone (CCl 3 C(O)CH 2 C(O)CH 3 ), hexachloroacetylacetone ( CCl3C (O) CH2C (O) CCl3 ), trifluoroacetylacetone ( CF3C (O) CH2C (O) CH3 ), hexafluoroacetylacetone (HFAc, CF3C (O) CH2) C(O)CF 3 ) may be used.
  • the first developer gas includes alcohol.
  • the alcohol may be nonafluoro-tert-butyl alcohol ((CF 3 ) 3 C-OH) in one example.
  • the first developer gas is a gas comprising trifluoroacetic acid.
  • the first development gas includes a halogenated organic acid vapor.
  • the first developer gas in one example, is selected from the group consisting of trifluoroacetic anhydride, acetic anhydride, trichloroacetic acid, CFH2COOH , CF2HCOOH , chlorodifluoroacetic acid, sulfur-containing acetic acid, and thioacetic acid and thioglycolic acid. including at least one.
  • the first developing gas is a mixed gas of carboxylic acid and hydrogen halide or a mixed gas of acetic acid and formic acid.
  • the first processing gas is a gas comprising acetic acid.
  • the second region RM2 of the resist film RM is removed at a first selection ratio with respect to the first region RM1.
  • the "selectivity" is also called development contrast, and is the ratio of the development speed of the second region RM2 to the development speed of the first region RM1.
  • the first selection ratio may be appropriately set to a range in which the second region RM2 is selectively removed with respect to the first region RM1 (that is, a value greater than 1).
  • the first selection ratio may be set relatively low to the extent that a portion of the first region RM1 is removed. In this case, even if there is a location other than the first region RM1 (location corresponding to the opening of the exposure mask) that has been exposed to EUV, the resist film at the location is removed to prevent the location from remaining as a residue. can.
  • Step ST120 may be performed until the second region RM2 is removed to a given depth or until the opening formed by development has a given aspect ratio.
  • the given depth or aspect ratio may be set based on the degree of progress of the exposure reaction in the first region RM1 (in one example, based on the thickness of the first portion RM1a and the second portion RM1b).
  • step ST120 may be performed until just before the second portion RM1b of the first region RM1 is exposed or until it is partially exposed.
  • FIG. 10 is a diagram showing an example of the cross-sectional structure of the substrate W after processing in step ST120.
  • the second region RM2 of the resist film RM is selectively removed with respect to the first region RM1, and the side surface of the first portion RM1a of the first region is exposed (the second portion RM1b are not exposed at this stage).
  • Step ST122 Developing with second selection ratio
  • a second processing gas containing a second developing gas is supplied into the processing chamber 102 through the gas nozzle 141.
  • the second developing gas may be the same as or different from step ST120.
  • step ST122 the second region RM2 of the resist film RM is removed with respect to the first region at a second selection ratio different from the first selection ratio.
  • the selection ratio can be made different from the first selection ratio by, for example, developing conditions such as the set temperature of the substrate W or the substrate support 11, the pressure inside the processing chamber 102, the type and concentration (partial pressure) of the processing gas, etc. This may be done by changing one or more of the above steps from step ST120.
  • the second selectivity ratio is higher than the first selectivity ratio.
  • the second selection ratio may be made higher than the first selection ratio by performing any one or more of the following (I) to (IV).
  • step ST122 the set temperature of the substrate W or substrate support portion 121 is set lower than in step ST120.
  • the set temperature of the substrate support part 121 in step ST120 may be set to 20°C or more and 60°C or less, or 40°C or more and 60°C or less, and the set temperature of the substrate support part 121 in step ST122 may be The set temperature may be set to -20°C or more and less than 20°C.
  • the set temperature of the substrate support part 121 in step ST120 may be 120°C or more and 180°C or less, and the set temperature of the substrate support part 121 in step ST122 may be set to 60°C.
  • the temperature may be lower than 120°C.
  • step ST122 the pressure inside the processing chamber 102 is lowered than in step ST120.
  • the pressure inside the chamber 102 in step ST120 may be set to 1 Torr or more and 10 Torr or less, and the pressure inside the processing chamber 102 in step ST122 may be set to 0.01 Torr or more and 1 Torr or less. .
  • step ST122 the acidity of the second developing gas is made lower than the acidity of the first developing gas. That is, in step ST122, a second developing gas having a larger acid dissociation constant (pKa) than the first developing gas used in step ST120 is used.
  • the developing gas may be changed from a gas containing a halogen-containing inorganic acid (step ST120) to a gas containing an organic acid (step ST122).
  • the developing gas may be changed from HBr gas or BCl 3 gas (step ST120) to carboxylic acid gas such as acetic acid gas (step ST122).
  • the developing gas may be changed from a gas containing a halogen-containing inorganic acid with high acidity (step ST120) to a gas containing a halogen-containing inorganic acid with low acidity (step ST122),
  • the gas containing an acid (step ST120) may be changed to a gas containing an organic acid with low acidity (step ST122).
  • the developing gas may be changed from HBr gas (step ST120) to BCl 3 gas (step ST122).
  • the flow rate (partial pressure) of "a gas with a relatively large acid dissociation constant (pKa)" in the mixed gas may be lowered in the second developing gas than in the first developing gas. may also be increased.
  • the flow rate (minute) of the carboxylic acid gas in the second developing gas is pressure
  • the flow rate (partial pressure) of the carboxylic acid gas in the first developing gas may be increased compared to the flow rate (partial pressure) of the carboxylic acid gas in the first developing gas.
  • step ST122 the concentration (partial pressure) of the developing gas in the processing gas is made lower than the concentration (partial pressure) of the developing gas in the processing gas in step ST120.
  • concentration (partial pressure) of the developing gas in step ST122 is lower than the concentration (partial pressure) of the developing gas in step 120.
  • Step ST122 may be performed until the second region RM2 is removed and the base film UF is exposed. Step ST122 may be performed until a portion of the base film UF is removed (overetched) in the depth direction.
  • FIG. 11 is a diagram showing an example of the cross-sectional structure of the substrate W after processing in step ST122.
  • the second region RM2 of the resist film RM is removed to form an opening OP.
  • the opening OP is defined by the side surface of the first region RM1.
  • the opening OP is a space above the base film UF surrounded by the side surface.
  • the opening OP has a shape corresponding to the second region RM2 (resultingly a shape corresponding to the exposure mask pattern used for EUV exposure) in a plan view of the substrate W.
  • the shape may be, for example, a circle, an ellipse, a rectangle, a line, or a combination of one or more of these shapes.
  • a plurality of openings OP may be formed in the resist film RM.
  • the plurality of openings OP each have a linear shape, and may be lined up at regular intervals to form a line-and-space pattern. Further, a plurality of openings OP may be arranged in a grid pattern to form a pillar pattern.
  • the first method includes a step ST120 of performing development at a first selection ratio, and a step ST122 of performing development at a second selection ratio different from the first selection ratio.
  • the shape of the developed pattern can be adjusted.
  • the second region RM2 can be removed with an appropriate selection ratio with respect to the first region RM1, and the pattern shape and roughness can be removed. Deterioration can be suppressed.
  • FIG. 12 is a flowchart of a modification of the first method. As shown in FIG. 12, step ST12 may include a step ST121 of modifying the resist film between step ST120 and step ST122.
  • a modification process is performed on the resist film RM.
  • the modification treatment is performed by heating the substrate W.
  • the heat treatment of the substrate W may be performed, for example, by controlling the output of one or more of the heaters of the heat treatment apparatus 100 to adjust the temperature of the substrate support part 121.
  • the substrate W may be heated to, for example, 180° C. or higher.
  • the substrate W may be heated to a temperature of, for example, 190° C. or more and 240° C. or less.
  • the substrate W may be heated to a temperature of, for example, 190° C. or more and 220° C. or less.
  • the inside of the chamber that heats the substrate W may be an atmosphere containing air, N 2 gas, and/or H 2 O gas.
  • the modification treatment increases the metal film density in the first region RM1 and can improve the development resistance. Since a portion of the second region RM2 is removed in step ST121 (see FIG. 10), modification is likely to proceed even in the portion RM1b of the first region RM1 where the exposure reaction is weak. This can suppress the development contrast from decreasing along the depth direction of the resist film RM.
  • the heat treatment in step ST121 may be performed in the processing chamber 102 of the heat treatment apparatus 100, which is different from step ST120 and step ST122. Further, the heat treatment in step ST121 may be performed using a device different from the heat treatment device 100.
  • the substrate W may be heated by irradiating the substrate W with electromagnetic waves using a device that generates electromagnetic waves such as infrared light or microwaves.
  • the modification treatment in step ST121 is performed by plasma treatment.
  • Plasma processing may be performed, for example, by transporting the substrate W from the heat treatment apparatus 100 to the plasma processing apparatus 1 and exposing the substrate W to plasma generated within the plasma processing apparatus 1.
  • Plasma processing may be performed, for example, by introducing a processing gas excited by a remote plasma source into the processing chamber 102 of the heat processing apparatus 100.
  • the processing gas for plasma generation may be an inert gas. Examples of the inert gas include noble gases such as He, Ar, Ne, Kr, and Xe, and nitrogen gas.
  • the first method may be performed using a plasma processing system (see FIGS. 2 and 3).
  • a plasma processing system see FIGS. 2 and 3
  • the resist film RM is Dry development may be performed (step ST12).
  • the processing gas may be the same as when using a heat treatment system.
  • a source RF signal may be supplied to the lower electrode of the substrate support 11 and/or the upper electrode of the shower head 13.
  • a bias signal may be supplied to the lower electrode of the substrate support section 11.
  • plasma is generated from the processing gas in the chamber 10, and active species such as ions and radicals in the plasma are attracted to the substrate W, thereby promoting development.
  • development may be performed in step ST122 at a second selection ratio different from the first selection ratio by changing any one or more of the development conditions from step ST120.
  • the development conditions to be changed include, for example, the set temperature of the substrate W or the substrate support 11, the pressure inside the processing chamber 10, the type and concentration (partial pressure) of the processing gas, the power level of the source RF signal, and the power level of the bias signal. or voltage level.
  • the second selectivity ratio may be made higher than the first selectivity ratio by, for example, performing any one or more of the following (I) to (IV) in step ST122. good.
  • step ST122 the set temperature of the substrate W or substrate support portion 11 is set lower than in step ST120.
  • the set temperature of the substrate support part 11 in step ST120 may be 20°C or more and 60°C or less, or 40°C or more and 60°C or less, and the set temperature of the substrate support part 11 in step ST122 may be set to The temperature may be -20°C or higher and lower than 20°C.
  • the set temperature of the substrate support part 11 in step ST120 may be set to 120°C or more and 180°C or less, and the set temperature of the substrate support part 121 in step ST122 may be set to 60°C or more and 120°C or less. It may be less than Note that the temperature of the substrate support portion 11 may be adjusted to a set temperature by a temperature control module. Further, the temperature of the substrate support portion 11 may be adjusted to a set temperature by controlling the pressure of heat transfer gas (for example, He) between the electrostatic chuck 1111 and the back surface of the substrate W.
  • heat transfer gas for example, He
  • step ST122 the pressure inside the processing chamber 10 is lowered than in step ST120.
  • the pressure in the processing chamber 10 in step ST120 may be set to 1 Torr or more and 10 Torr or less, and the pressure in the processing chamber 10 in step ST122 may be set to 0.01 Torr or more and 1 Torr or less.
  • step ST122 the acidity of the second developing gas is made lower than the acidity of the first developing gas. That is, in step ST122, a second developing gas having a larger acid dissociation constant (pKa) than the first developing gas used in step ST120 is used.
  • the developing gas may be changed from a gas containing a halogen-containing inorganic acid (step ST120) to a gas containing an organic acid (step ST122).
  • the developing gas may be changed from HBr gas or BCl 3 (step ST120) to a carboxylic acid gas such as acetic acid gas (step ST122).
  • the developing gas may be changed from a gas containing a halogen-containing inorganic acid with high acidity (step ST120) to a gas containing a halogen-containing inorganic acid with low acidity (step ST122),
  • the gas containing an acid (step ST120) may be changed to a gas containing an organic acid with low acidity (step ST122).
  • the developing gas may be changed from HBr gas (step ST120) to BCl 3 gas (step ST122).
  • the flow rate (partial pressure) of "a gas with a relatively large acid dissociation constant (pKa)" in the mixed gas may be lowered in the second developing gas than in the first developing gas. may also be increased.
  • the flow rate (minute) of the carboxylic acid gas in the second developing gas is pressure
  • the flow rate (partial pressure) of the carboxylic acid gas in the first developing gas may be increased compared to the flow rate (partial pressure) of the carboxylic acid gas in the first developing gas.
  • step ST122 the concentration (partial pressure) of the developing gas in the processing gas is made lower than the concentration (partial pressure) of the developing gas in the processing gas in step ST120.
  • concentration (partial pressure) of the developing gas in step ST122 is lower than the concentration (partial pressure) of the developing gas in step 120.
  • step ST120 and step ST122 When generating plasma from the processing gas in step ST120 and step ST122, at least one of the following (V) and (VI) may be performed in addition to or in place of the above (I) to (IV). Thereby, the second selection ratio may be higher than the first selection ratio.
  • step ST122 the power level of the source RF signal supplied to the chamber 10 is made lower than the power level of the source RF signal in step ST120.
  • step ST122 the power or voltage level of the bias signal supplied to the chamber 10 is made smaller than the power or voltage level of the bias signal in step ST120.
  • the first method may include a desorption step.
  • the desorption step includes descuming the surface of the resist film RM or smoothing the surface of the resist film RM using an inert gas such as helium or a plasma of the inert gas.
  • the desorption step may be performed after step ST12.
  • the desorption step may be repeated one or more times between step ST120 and step ST122.
  • the desorption step may be performed instead of between step ST120 and step ST122, or between step ST120 and step ST122, and before step ST12 (step ST122) and the step of etching the base film UF, which will be described later. It's okay.
  • the first method may be performed in a liquid processing system (see FIG. 4). That is, a substrate is provided to the spin chuck 311 in the processing chamber 310 of the liquid processing apparatus 300 (step ST11), and a developing solution is supplied to the substrate W from the processing solution supply nozzle 331, thereby performing wet development of the resist film RM. (Step ST12) You may do as follows.
  • Examples of the developer include aromatic compounds such as benzene, xylene, and toluene, esters such as propylene glycol monomethyl ester acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, 4-methyl-2-pentanol, 1- It may include alcohols such as butanol, isopropanol, 1-propanol and methanol, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone and 2-octanone, and ethers such as tetrahydrofuran, dioxane and anisole.
  • aromatic compounds such as benzene, xylene, and toluene
  • esters such as propylene glycol monomethyl ester acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone,
  • step ST122 When using a liquid processing system, in step ST122, for example, by changing one or more of the solubility, concentration, and temperature of the developer from step ST120, development is performed at a second selection ratio different from the first selection ratio. You may do so.
  • the second selection ratio may be made higher than the first selection ratio by, for example, performing any one or more of the following (I) to (III) in step ST122. good.
  • the concentration of the developer used in step ST122 is made lower than the concentration of the developer used in step ST120, for example by increasing the dilution of the developer.
  • the temperature of the developer used in step ST122 is lower than the temperature of the developer used in step ST120.
  • the temperature of the developer may be controlled to be 30°C or more and 90°C or less
  • the temperature of the developer may be controlled to be 10°C or more and 60°C or less.
  • the development process in step ST12 may be performed by both dry development and wet development.
  • step ST120 is performed by wet development using a liquid processing system (see FIG. 4)
  • step ST122 is performed by dry development using a heat processing system (see FIG. 1) or a plasma processing system (see FIGS. 2 and 3). This may be carried out by development.
  • wet development is performed before dry development, it is possible to suppress the occurrence of contamination due to the developer seeping into the base film UF and pattern collapse of the resist film due to the surface tension of the developer.
  • step ST120 may be performed by dry development
  • step ST122 may be performed by wet development.
  • the development treatment in step ST12 may be performed using both heat treatment and plasma treatment.
  • step ST120 may be performed by heat treatment and step ST122 may be performed by plasma treatment
  • step ST120 may be performed by plasma treatment and step ST122 may be performed by heat treatment.
  • a cycle including step ST120 and step ST122 may be repeated multiple times.
  • the cycle of step ST120 and step ST122 may be repeated multiple times using only dry development, or may be repeated multiple times using only wet development.
  • the cycle of Step ST120 and Step ST122 may be performed one or more times by dry development.
  • the cycle of step ST120 performed by wet development and step ST122 performed by dry development may be repeated multiple times.
  • the development conditions of step ST120 and/or step ST122 may be different from one or more cycles to another one or more cycles. It can be different.
  • the temperature of the substrate support portion in step ST120 may be lower in one or more cycles in which development is performed to a second depth deeper than the first depth than in one or more cycles in which development is performed to a first depth.
  • the base film UF is etched after step ST12.
  • the etching process may be performed, for example, by generating plasma from a process gas in the process chamber 10 of the plasma processing apparatus 1.
  • the resist film RM functions as a mask, and a recess is formed in the base film UF based on the shape of the opening OP.
  • the etching process may be performed continuously in the same processing chamber 10 as in step ST12, or in the processing chamber 10 of another plasma processing apparatus 1. It may be executed within.
  • FIG. 13 is a flowchart showing a substrate processing method (hereinafter also referred to as "second method") according to the second exemplary embodiment. As shown in FIG. 13, the second method includes a step ST21 of providing a substrate and a step ST22 of developing the substrate.
  • the development process in step ST22 is performed by dry development. In one embodiment, the development process in step ST22 is performed by wet development. In one embodiment, the development process in step ST22 is performed using both wet development and dry development.
  • the second method may be performed in the heat treatment system described above (FIG. 1).
  • the control section 200 controls each section of the heat treatment apparatus 100 to perform the second method on the substrate W will be described as an example.
  • the second method may be performed by combining the thermal processing system (FIG. 1) with other substrate processing systems, such as a plasma processing system (FIGS. 2 and 3) or a liquid processing system (FIG. 4).
  • Step ST21 the substrate W is provided in the processing chamber 102 of the heat processing apparatus 100.
  • Step ST21 is similar to step ST11 of the first method, and the structure of the substrate W may be the same as that shown in FIG. 6.
  • Step ST22 Development of substrate
  • the resist film RM on the substrate W is developed, and the first region RM1 is selectively removed.
  • Step ST22 includes a step ST220 of developing the substrate with a first selectivity ratio, and a step ST222 of developing the substrate with a second selectivity ratio different from the first selectivity ratio.
  • Step ST220 Developing with the first selection ratio
  • a processing gas containing a developing gas is supplied into the processing chamber 102 through the gas nozzle 141.
  • the developing gas may be a gas that can selectively remove the first region with respect to the second region, unlike in step ST120 of the first method described above. As a result, the first region RM1 of the resist film RM is selectively removed with respect to the second region RM2.
  • the first region RM1 of the resist film RM is removed at a first selection ratio with respect to the second region RM2.
  • the "selectivity" is also called development contrast, and is the ratio of the development speed of the first region RM1 to the development speed of the second region RM2.
  • the first selection ratio may be appropriately set within a range in which the first region RM1 is selectively removed with respect to the second region RM2 (that is, a value greater than 1).
  • Step ST220 may be performed until the first region RM1 is removed to a given depth or until the opening formed by development has a given aspect ratio.
  • the given depth or aspect ratio may be set based on the degree of progress of the exposure reaction in the first region RM (in one example, based on the thickness of the first portion RM1a and the second portion RM1b).
  • step ST220 may be performed until just before the second portion RM1b of the first region RM1 is removed or until it is partially removed.
  • FIG. 14 is a diagram showing an example of the cross-sectional structure of the substrate W after processing in step ST220.
  • the first region RM1 of the resist film RM is selectively removed with respect to the second region RM2, and the upper surface of the second portion RM1b of the first region is exposed.
  • Step ST222 Developing with second selection ratio
  • a processing gas containing a developing gas is supplied into the processing chamber 102 through the gas nozzle 141.
  • the developing gas may be the same as or different from the developing gas used in step ST220.
  • the first region RM1 of the resist film RM is selectively etched with respect to the second region RM2.
  • step ST222 the first region RM1 of the resist film RM is removed with respect to the second region RM2 at a second selection ratio different from the first selection ratio.
  • the selection ratio can be made different from the first selection ratio by, for example, developing conditions such as the set temperature of the substrate W or the substrate support 11, the pressure inside the processing chamber 102, the type and concentration (partial pressure) of the processing gas, etc. This may be done by changing one or more of the above steps from step ST220.
  • the second selectivity ratio is higher than the first selectivity ratio.
  • the second selection ratio may be made higher than the first selection ratio by performing any one or more of the following (I) to (IV).
  • step ST222 the set temperature of the substrate W or substrate support portion 121 is set lower than in step ST220.
  • step ST222 the pressure inside the processing chamber 102 is made higher than in step ST220.
  • step ST222 the acidity of the developing gas is made greater than the acidity of the developing gas in step ST220.
  • step ST222 the concentration (partial pressure) of the developing gas in the processing gas is made higher than the concentration (partial pressure) of the developing gas in the processing gas in step ST220.
  • Step ST222 may be performed until the first region RM1 is removed and the base film UF is exposed. Step ST222 may be performed until a portion of the base film UF is removed (overetched) in the depth direction.
  • FIG. 15 is a diagram showing an example of the cross-sectional structure of the substrate W after processing in step ST222.
  • the first region RM1 of the resist film RM is removed to form an opening OP.
  • the opening OP is defined by the side surface of the second region RM2.
  • the opening OP is a space above the base film UF surrounded by the side surface.
  • the opening OP has a shape corresponding to the first region RM1 (resultingly, a shape corresponding to the opening of the exposure mask used for EUV exposure) in a plan view of the substrate W.
  • the shape may be, for example, a circle, an ellipse, a rectangle, a line, or a combination of one or more of these shapes.
  • a plurality of openings OP may be formed in the resist film RM.
  • the plurality of openings OP each have a hole shape and may constitute an array pattern arranged at regular intervals. Further, the plurality of openings OP each have a linear shape, and may be lined up at regular intervals to form a line-and-space pattern.
  • a developed pattern consisting of the unexposed second region RM2 can be formed by the development process.
  • a pattern for example, a hole array pattern
  • the second method includes a step ST220 of performing development at a first selection ratio, and a step ST222 of performing development at a second selection ratio different from the first selection ratio.
  • This allows the shape of the developed pattern to be adjusted.
  • the first region RM1 can be removed with an appropriate selection ratio relative to the second region RM2, and the pattern shape and roughness can be removed. Deterioration can be suppressed.
  • the development process in step ST22 may be performed using a plasma processing apparatus system (see FIGS. 2 and 3) and/or a liquid processing system (see FIG. 4), similarly to step ST12.
  • the second method may include a desorption step similarly to the first method. The desorption step may be performed after step ST22, or may be repeatedly performed one or more times between the developments in step ST22.
  • the development treatment in step ST22 may be performed using both heat treatment and plasma treatment.
  • step ST220 may be performed by heat treatment
  • step ST222 may be performed by plasma treatment
  • step ST220 may be performed by plasma treatment
  • step ST222 may be performed by heat treatment.
  • a cycle including step ST220 and step ST222 may be repeated multiple times.
  • the cycle of step ST220 and step ST222 may be repeated multiple times using only dry development, or may be repeated multiple times using only wet development.
  • the cycle of steps ST220 and ST222 may be performed one or more times by dry development.
  • the cycle of step ST220 performed by wet development and step ST222 performed by dry development may be repeated multiple times.
  • the development conditions of step ST220 and/or step ST222 may be changed between one or more cycles and another one or more cycles. It can be different.
  • the temperature of the substrate support portion in step ST220 may be lower in one or more cycles in which development is performed to a second depth deeper than the first depth than in one or more cycles in which development is performed to a first depth.
  • the base film UF is etched after step ST22.
  • the etching process may be performed, for example, by generating plasma from a process gas in the process chamber 10 of the plasma processing apparatus 1.
  • the resist film RM functions as a mask, and a recess is formed in the base film UF based on the shape of the opening OP.
  • the etching process may be performed continuously in the same processing chamber 10 as in step ST22, or in the processing chamber 10 of another plasma processing apparatus 1. It may be executed within.
  • FIG. 16 is a block diagram for explaining a configuration example of the substrate processing system SS according to the exemplary embodiment.
  • the substrate processing system SS includes a first carrier station CS1, a first processing station PS1, a first interface station IS1, an exposure apparatus EX, a second interface station IS2, and a second processing station PS2. , a second carrier station CS2, and a controller CT.
  • the first carrier station CS1 carries in and out the first carrier C1 between the first carrier station CS1 and a system outside the substrate processing system SS.
  • the first carrier station CS1 has a mounting table including a plurality of first mounting plates ST1. On each first mounting plate ST1, a first carrier C1 containing a plurality of substrates W or empty is mounted.
  • the first carrier C1 has a casing that can house a plurality of substrates W therein.
  • the first carrier C1 is, for example, a FOUP (Front Opening Unified Pod).
  • the first carrier station CS1 transports the substrate W between the first carrier C1 and the first processing station PS1.
  • the first carrier station CS1 further includes a first transport device HD1.
  • the first transport device HD1 is provided in the first carrier station CS1 so as to be located between the mounting table and the first processing station PS1.
  • the first transport device HD1 transports and transfers the substrate W between the first carrier C1 on each first mounting plate ST1 and the second transport device HD2 of the first processing station PS1.
  • the substrate processing system SS may further include a load lock module.
  • a load lock module may be provided between the first carrier station CS1 and the first processing station PS1.
  • the load lock module can switch its internal pressure to atmospheric pressure or vacuum. "Atmospheric pressure" may be the pressure inside the first transport device HD1.
  • “Vacuum” is a pressure lower than atmospheric pressure, and may be a medium vacuum of, for example, 0.1 Pa to 100 Pa.
  • the interior of the second transport device HD2 may be at atmospheric pressure or vacuum.
  • the load lock module transports the substrate W from the first transport device HD1 at atmospheric pressure to the second transport device HD2 at vacuum, and from the second transport device HD2 at vacuum to the second transport device HD2 at atmospheric pressure.
  • the substrate W may be transported to the No. 1 transport device HD1.
  • the first processing station PS1 performs various processing on the substrate W.
  • the first processing station PS1 includes a pre-processing module PM1, a resist film forming module PM2, and a first heat processing module PM3 (hereinafter also referred to as "first substrate processing module PMa").
  • the first processing station PS1 includes a second transport device HD2 that transports the substrate W.
  • the second transport device HD2 transfers substrates between two specified first substrate processing modules PMa, and between the first processing station PS1 and the first carrier station CS1 or the first interface station IS1. Transports and delivers W.
  • the substrate W is subjected to pre-processing.
  • the preprocessing module PM1 includes a temperature adjustment unit that adjusts the temperature of the substrate W, a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision, and the like.
  • the pretreatment module PM1 includes a surface modification treatment unit that performs a surface modification treatment on the substrate W.
  • Each processing unit of the pretreatment module PM1 may include a heat treatment apparatus 100 (see FIG. 1), a plasma treatment apparatus 1 (see FIGS. 2 and 3), and/or a liquid treatment apparatus 300 (see FIG. 4). .
  • the resist film forming module PM2 includes a dry coating unit.
  • the dry coating unit forms a resist film on the substrate W using a dry process such as a vapor deposition method.
  • the dry coating unit includes, for example, a CVD device or an ALD device that chemically vapor deposits a resist film, or a PVD device that physically vapor deposits a resist film on a substrate W disposed in a chamber.
  • the dry coating unit may be a heat treatment apparatus 100 (see FIG. 1) or a plasma treatment apparatus 1 (see FIGS. 2 and 3).
  • the resist film forming module PM2 includes a wet coating unit.
  • the wet coating unit forms a resist film on the substrate W using a wet process such as a liquid phase deposition method.
  • the wet coating unit may be, for example, a liquid processing device 300 (see FIG. 4).
  • the example resist film forming module PM2 includes both a wet coating unit and a dry coating unit.
  • the substrate W is subjected to heat treatment.
  • the first heat treatment module PM3 includes a pre-bake (PAB) unit that performs heat treatment on the substrate W on which a resist film is formed, a temperature adjustment unit that adjusts the temperature of the substrate W, and a temperature adjustment unit that adjusts the temperature of the substrate W with high precision.
  • the temperature control unit includes one or more high-precision temperature control units. Each of these units may each have one or more heat treatment devices. In one example, multiple heat treatment devices may be stacked.
  • the heat treatment apparatus may be, for example, the heat treatment apparatus 100 (see FIG. 1). Each heat treatment may be performed at a predetermined temperature using a predetermined gas.
  • the first interface station IS1 has 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 apparatus EX.
  • the third transport device HD3 has a casing that accommodates the substrate W, and may be configured to be able to control the temperature, humidity, pressure, etc. inside the casing.
  • the exposure apparatus EX exposes the resist film on the substrate W using an exposure mask (reticle).
  • the exposure apparatus EX may be, for example, an EUV exposure apparatus having a light source that generates EUV light.
  • the second interface station IS2 has a fourth transport device HD4.
  • the fourth transport device HD4 transports and transfers the substrate W between the exposure apparatus EX and the second processing station PS2.
  • the fourth transport device HD4 may have a casing that accommodates the substrate W, and may be configured to be able to control the temperature, humidity, pressure, etc. within the casing.
  • the second processing station PS2 performs various processing on the substrate W.
  • the second processing station PS2 includes a second heat treatment module PM4, a measurement module PM5, a development module PM6, and a third heat treatment module PM7 (hereinafter also collectively referred to as "second substrate processing module PMb").
  • the second processing station PS2 includes a fifth transport device HD5 that transports the substrate W.
  • the fifth transport device HD5 transports substrates between two specified second substrate processing modules PMb and between the second processing station PS2 and the second carrier station CS2 or the second interface station IS2. Transports and delivers W.
  • the substrate W is subjected to heat treatment.
  • the heat treatment module PM4 includes a post-exposure bake (PEB) unit that heat-treats the substrate W after exposure, a temperature adjustment unit that adjusts the temperature of the substrate W, and a heat treatment module that adjusts the temperature of the substrate W with high precision. It includes one or more precision temperature control units. Each of these units may each have one or more heat treatment devices. In one example, multiple heat treatment devices may be stacked.
  • the heat treatment apparatus may be, for example, the heat treatment apparatus 100 (see FIG. 1). Each heat treatment may be performed at a predetermined temperature using a predetermined gas.
  • the measurement module PM5 includes an imaging unit including a mounting table on which the substrate W is placed, an imaging device, an illumination device, and various sensors (temperature sensor, reflectance measurement sensor, etc.).
  • the imaging device may be, for example, a CCD camera that images the appearance of the substrate W.
  • the imaging device may be a hyperspectral camera that separates light into wavelengths and photographs the images.
  • the hyperspectral camera can measure any one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film.
  • the substrate W is subjected to development processing.
  • the development module PM6 includes a dry development unit that performs dry development on the substrate W.
  • the dry development unit may be, for example, a thermal processing apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).
  • the development module PM6 includes a wet development unit that performs wet development on the substrate W.
  • the wet development unit may be, for example, the liquid processing apparatus 300 (FIG. 4).
  • development module PM6 includes both a dry development unit and a wet development unit.
  • the substrate W is subjected to heat treatment.
  • the third heat treatment module PM7 includes a post bake (PB) unit that heats the substrate W after development, a temperature adjustment unit that adjusts the temperature of the substrate W, and a temperature adjustment unit that increases the temperature of the substrate W. It includes one or more high-precision temperature control units that adjust accurately. Each of these units may each have one or more heat treatment devices. In one example, multiple heat treatment devices may be stacked.
  • the heat treatment apparatus may be, for example, the heat treatment apparatus 100 (see FIG. 1). Each heat treatment may be performed at a predetermined temperature using a predetermined gas.
  • the second carrier station CS2 carries in and out the second carrier C2 between the second carrier station CS2 and a system external to the substrate processing system SS.
  • the configuration and function of the second carrier station CS2 may be similar to the first carrier station CS1 described above.
  • the control unit CT controls each component of the substrate processing system SS to perform a given process on the substrate W.
  • the control unit CT stores recipes in which process procedures, process conditions, transport conditions, etc. Control configuration.
  • the control unit CT may serve as part or all of the functions of each control unit (control unit 200, control unit 2, and control unit 400 shown in FIGS. 1 to 4).
  • FIG. 17 is a flowchart illustrating a substrate processing method (hereinafter also referred to as "method MT") according to an exemplary embodiment.
  • the method MT includes a step ST100 of pre-processing the substrate, a step ST200 of forming a resist film on the substrate, and a step ST200 of performing heat treatment (pre-bake: PAB) on the substrate on which the resist film is formed.
  • PEB post-exposure bake
  • the process includes ST700, a step ST800 of performing heat treatment (post-bake: PB) on the substrate after development, and a step ST900 of etching the substrate.
  • Method MT may not include one or more of the above steps.
  • method MT may not include step ST600, and step ST700 may be performed after step ST500.
  • Method MT may be performed using the substrate processing system SS shown in FIG. 16.
  • the control unit CT of the substrate processing system SS controls each part of the substrate processing system SS to execute the method MT on the substrate W will be described as an example.
  • the first carrier C1 containing a plurality of substrates W is carried into the first carrier station CS1 of the substrate processing system SS.
  • the first carrier C1 is mounted on the first mounting plate ST1.
  • each substrate W in the first carrier C1 is sequentially taken out by the first transport device HD1 and delivered to the second transport device HD2 of the first processing station PS1.
  • the substrate W is transported to the preprocessing module PM1 by the second transport device HD2.
  • the preprocessing module PM1 performs preprocessing on the substrate W.
  • the pretreatment may include, for example, one or more of temperature adjustment of the substrate W, formation of part or all of the base film of the substrate W, heat treatment of the substrate W, and high-precision temperature adjustment of the substrate W.
  • the pretreatment may include surface modification treatment of the substrate W.
  • 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.
  • the formation of the resist film is performed by a wet process such as liquid deposition.
  • a resist film is formed by spin coating a resist film on the substrate W using the wet coating unit of the resist film forming module PM2.
  • the resist film is formed on the substrate W by a dry process such as a vapor deposition method.
  • a resist film is formed by depositing a resist film on the substrate W using the dry coating unit of the resist film forming module PM2.
  • the formation of the resist film on the substrate W may be performed using both a dry process and a wet process.
  • a second resist film may be formed on the first resist film by a wet process.
  • the film thickness, material, and/or composition of the first resist film and the second resist film may be the same or different.
  • the substrate W is transported to the first heat treatment module PM3 by the second transport device HD2.
  • the first heat treatment module PM3 performs heat treatment (pre-bake: PAB) on the substrate W.
  • Prebaking may be performed in an air atmosphere or in an inert atmosphere. Further, the prebaking may be performed by heating the substrate W to 50° C. or higher or 80° C. or higher.
  • the heating temperature of the substrate W may be 250°C or lower, 200°C or lower, or 150°C or lower. In one example, the heating temperature of the substrate may be 50° C. or higher and 250° C. or lower.
  • prebaking may be continuously performed in the dry coating unit that performed step ST200.
  • a process for removing the resist film at the edge of the substrate W (Edge Bead Removal: EBR) may be performed.
  • the substrate W is transferred by the second transport device HD2 to the third transport device HD3 of the first interface station IS1.
  • the substrate W is then transported to the exposure apparatus EX by the third transport device HD3.
  • the substrate W receives EUV exposure through an exposure mask (reticle) in the exposure apparatus EX.
  • a first region exposed to EUV light and a second region not exposed to EUV light are formed on the substrate W, corresponding to the pattern of the exposure mask (reticle).
  • the substrate W is transferred from the fourth transport device HD4 of the second interface station IS2 to the fifth transport device HD5 of the second processing station PS2.
  • the substrate W is then transported to the second heat treatment module PM4 by the fifth transport device HD5.
  • the substrate W is subjected to heat treatment (post-exposure bake: PEB) in the second heat treatment module PM4.
  • the post-exposure bake may be performed in an atmospheric atmosphere. Further, the post-exposure bake may be performed by heating the substrate W to a temperature of 180° C. or higher and 250° C. or lower.
  • the substrate W is transported to the measurement module PM5 by the fifth transport device HD5.
  • the measurement module PM5 measures the substrate W.
  • the measurements may be optical measurements or other measurements.
  • the measurements by the measurement module PM5 include measurements of the appearance and/or dimensions of the substrate W using a CCD camera.
  • the measurement module PM5 measures any one or more of the pattern shape, dimensions, film thickness, composition, and film density (hereinafter also referred to as "pattern shape, etc.") of the resist film using a hyperspectral camera. Including measurements.
  • control unit CT determines whether or not there is an exposure abnormality in the substrate W based on the measured appearance, dimensions, and/or pattern shape of the substrate W. In one embodiment, if the control unit CT determines that there is an exposure abnormality, the substrate W may be reworked or discarded without performing development in step ST700. Rework of the substrate W may be performed by removing the resist on the substrate W and returning to step ST200 again to form a resist film. Although rework after development may involve damage to the substrate W, damage to the substrate W can be avoided or suppressed by performing rework before development.
  • the development process may be performed by dry development or wet development.
  • the development process may be performed using a combination of dry development and wet development.
  • the development process in step ST700 may be performed by the first method (see FIGS. 5 and 11) or the second method (see FIG. 12).
  • a desorption process may be performed one or more times after or during the development process.
  • the desorption process includes descuming or smoothing the surface of the resist film with an inert gas such as helium or a plasma of the inert gas.
  • an inert gas such as helium or a plasma of the inert gas.
  • the substrate W is transported to the third heat treatment module PM7 by the fifth transport device HD5, and is subjected to heat treatment (post-bake).
  • Post-baking may be performed in an atmospheric atmosphere or in a reduced pressure atmosphere containing N 2 or O 2 . Further, post-baking may be performed by heating the substrate W to 150° C. or higher and 250° C. or lower.
  • Post-baking may be performed by the second heat treatment module PM4 instead of the third heat treatment module PM7.
  • optical measurements of the substrate W may be made by a measurement module PM4PM5. Such measurements may be performed in addition to or in place of the measurements in step ST600.
  • the control unit CT determines whether or not there are abnormalities such as defects, scratches, and adhesion of foreign substances in the developed pattern of the substrate W based on the measured appearance, dimensions, and/or pattern shape of the substrate W. etc. are determined. In one embodiment, if the controller CT determines that there is an abnormality, the substrate W may be reworked or discarded without performing etching in step ST900. In one embodiment, if the control unit CT determines that there is an abnormality, the opening size of the resist film of the substrate W may be adjusted using a dry coating unit (CVD device, ALD device, etc.).
  • the substrate W is transferred by the fifth transfer device HD5 to the sixth transfer device HD6 of the second carrier station CS2, and the substrate W is transferred to the sixth transfer device HD6 of the second carrier station CS2 by the sixth transfer device HD6. It is transported to the second carrier C2.
  • the second carrier C2 is then transported to a plasma processing system (not shown).
  • the plasma processing system may be, for example, the plasma processing system shown in FIGS. 2 and 3.
  • the base film UF of the substrate W is etched using the developed resist film as a mask. With this, the method MT ends.
  • etching may be continuously performed within the plasma processing chamber of the plasma processing apparatus. Furthermore, if the second processing station PS2 includes a plasma processing module in addition to the development module PM6, the etching may be performed within the plasma processing module.
  • the desorption process described above may be performed one or more times before or during etching.
  • Embodiments of the present disclosure further include the following aspects.
  • a substrate processing method comprising: (a) providing a substrate having a base film and a metal-containing resist film on the base film on a substrate support, the metal-containing resist film including a first region and a second region; process and (b) developing the metal-containing resist film to selectively remove the second region from the metal-containing resist film;
  • the step (b) above is (b1) removing the second region with respect to the first region at a first selection ratio; (b2) further removing the second region with respect to the first region at a second selection ratio different from the first selection ratio; Substrate processing method.
  • step (b) the development is performed by wet development,
  • the step (b) above is (I) The solubility of the metal-containing resist film in the developer used in the step (b2) is lower than the solubility of the metal-containing resist film in the developer used in the step (b1); (II) The concentration of the developer used in the step (b2) is lower than the concentration of the developer used in the step (b1), and (III) The temperature of the developer used in the step (b2) is lower than the temperature of the developer used in the step (b1);
  • the substrate processing method according to any one of Supplementary Notes 1 to 3, which satisfies at least one of the following.
  • step (b) In the step (b), the development is performed by dry development in a chamber,
  • the step (b) above is (I) The temperature of the substrate support portion in the step (b2) is lower than the temperature of the substrate support portion in the step (b1); (II) The pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1); (III) The acidity of the second developing gas used in the step (b2) is lower than the acidity of the first developing gas used in the step (b1), and (IV) The concentration of the second developing gas used in the step (b2) is lower than the concentration of the first developing gas used in the step (b1);
  • the substrate processing method according to any one of Supplementary Notes 1 to 3, which satisfies at least one of the following.
  • the above (b1) is performed by dry development using a first processing gas containing a first developing gas
  • the above (b2) is performed by dry development using a second processing gas containing a second developing gas
  • the step (b) above is (I) The temperature of the substrate support portion in the step (b2) is lower than the temperature of the substrate support portion in the step (b1); (II) The pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1); (III) the acidity of the second developing gas is lower than the acidity of the first developing gas; (IV) the concentration of the second developing gas is lower than the concentration of the first developing gas; and (V)
  • the second processing gas includes a protective gas that protects the side wall of the first region exposed in the step (b1) and the step (b2), and the first processing gas includes the Containing no protective gas or containing the protective gas at a lower partial pressure than (the partial pressure of) the protective gas contained in the second processing gas;
  • step (b) the development is performed by dry development using plasma generated in a chamber
  • the step (b) above is (I) The power level of the source RF signal for plasma generation supplied to the chamber in the step (b2) is lower than the power level of the source RF signal in the step (b1), and (II) The power or voltage level of the bias signal supplied to the chamber in the step (b2) is smaller than the power or voltage level of the bias signal in the step (b1);
  • the substrate processing method according to any one of Supplementary Notes 1 to 3, which satisfies at least one of the following.
  • the step (b) further includes a step of modifying the first region between the step (b1) and the step (b2), according to any one of Supplementary notes 1 to 7.
  • Appendix 14 The substrate processing method according to any one of appendices 1 to 13, wherein the metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti.
  • Appendix 15 The substrate processing method according to any one of appendices 1 to 14, wherein the first region is exposed to EUV light.
  • the first region includes a first portion and a second portion below the first portion and on the base film,
  • the substrate processing method according to any one of Supplementary notes 1 to 16, wherein the step (b1) is performed until immediately before the second portion is exposed, or until a part of the second portion is exposed. .
  • a substrate processing method comprising: (a) providing on a substrate support a substrate having a base film and a metal-containing resist film formed on the base film, the metal-containing resist film being in contact with the exposed first region; a second region in which the second region is not (b) selectively removing the second region from the metal-containing resist film by dry developing the metal-containing resist film;
  • the step (b) above is (b1) controlling the temperature of the substrate support part to a first temperature and removing the second region; (b2) controlling the temperature of the substrate support part to a second temperature lower than the first temperature and removing the second region; Substrate processing method.
  • the step (b) is a step of dry developing using HBr, the first temperature is 20°C or more and 60°C or less, and the second temperature is -20°C or more and 20°C or less.
  • a substrate processing method comprising: (a) providing on a substrate support a substrate having a base film and a metal-containing resist film formed on the base film, the metal-containing resist film being in contact with the exposed first region; a second region in which the second region is not (b) selectively removing the second region from the metal-containing resist film by dry developing the metal-containing resist film;
  • the step (b) above is (b1) using a first processing gas to remove the second region; (b2) removing the second region using a second processing gas having lower acidity than the first processing gas; Substrate processing method.
  • the first processing gas contains a halogen-containing inorganic acid
  • the second processing gas contains an organic acid. Substrate processing method according to appendix 24.
  • the first processing gas includes a halogen-containing inorganic acid and an organic acid at a lower flow rate than the halogen-containing inorganic acid
  • the second processing gas includes a halogen-containing inorganic acid and an organic acid at a higher flow rate than the halogen-containing inorganic acid.
  • halogen-containing inorganic acid includes at least one selected from the group consisting of HBr gas, HCl gas, BCl 3 gas, HF gas, and HI gas.
  • the step (b) above is (I) The temperature of the substrate support part in the step (b2) is lower than the temperature of the substrate support part in the step (b1), and (II) The temperature of the substrate support part in the step (b2) is lower than the temperature of the substrate support part in the step (b2).
  • step (b) In the step (b), after the cycle including the step (b1) and the step (b2) is performed one or more times, the step (b1) is further performed, Supplementary notes 24 to Supplementary notes 30.
  • the substrate processing method according to any one of 30.
  • step (b) is performed after the cycle including the step (b1) and the step (b2) is performed one or more times without using plasma. removing the second region using plasma generated from a second processing gas; The substrate processing method according to any one of attachments 24 to 31.
  • a substrate processing system comprising one or more substrate processing apparatuses and a control section
  • the control unit may cause the one or more substrate processing apparatuses to: (a) A control for providing a substrate having a base film and a metal-containing resist film on the base film on a substrate support, wherein the metal-containing resist film includes a first region and a second region. and, (b) control for selectively removing the second region from the metal-containing resist film by developing the metal-containing resist film;
  • the control in (b) above is (b1) control to remove the second region with respect to the first region at a first selection ratio; (b2) further removing the second region from the first region at a second selection ratio different from the first selection ratio; Substrate processing system.

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