Dry developing method and dry developing apparatus

Abstract

The present disclosure provides a technique capable of appropriately developing a metal-containing resist.SOLUTION: In one exemplary embodiment, the dry developing method includes (a) providing a substrate on a substrate support in a chamber, the substrate including a base film and a metal-containing resist on the base film, the metal-containing resist having an exposed first region and an unexposed second region, (b) forming a metal fluoride layer on a surface of the second region by supplying a first processing gas including a fluorine-containing gas into the chamber, and (c) removing the metal fluoride layer by supplying a second processing gas including a chlorine-containing gas into the chamber.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] SUMMARY OF THE INVENTION Exemplary embodiments of the present disclosure relate to a dry development method and a dry development apparatus. [Background technology]

[0002] Patent Document 1 discloses a technique for forming a metal-containing film on a semiconductor substrate that can be patterned using extreme ultraviolet light (hereinafter referred to as "EUV"), and a technique for selectively removing unexposed regions that have not been exposed to EUV using boron trichloride. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2021-523403 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides techniques that allow for proper development of metal-containing resists. [Means for solving the problem]

[0005] In one exemplary embodiment, a dry development method includes: (a) providing a substrate on a substrate support in a chamber, the substrate comprising an undercoat film and a metal-containing resist on the undercoat film, the metal-containing resist having a first exposed region and a second unexposed region; (b) forming a metal fluoride layer on a surface of the second region by supplying a first process gas containing a fluorine-containing gas into the chamber; and (c) removing the metal fluoride layer by supplying a second process gas containing a chlorine-containing gas into the chamber. [Effects of the Invention]

[0006] According to one exemplary embodiment, a technique is provided that allows for proper development of metal-containing resists. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram of a dry development apparatus according to one exemplary embodiment. [Figure 2] FIG. 2 is a schematic diagram of a dry development apparatus according to another exemplary embodiment. [Figure 3] FIG. 3 is a schematic diagram of a dry development apparatus according to another exemplary embodiment. [Figure 4] FIG. 4 is a flow chart of a dry development method according to one exemplary embodiment. [Figure 5] FIG. 5 is a cross-sectional view of an example substrate to which the method of FIG. 4 can be applied. [Figure 6] FIG. 6 is a cross-sectional view of another example substrate to which the method of FIG. 4 can be applied. [Figure 7] FIG. 7 is a cross-sectional view of another example substrate to which the method of FIG. 4 can be applied. [Figure 8] FIG. 8 is a cross-sectional view illustrating a step of a dry development method according to an exemplary embodiment. [Figure 9] FIG. 9 is a cross-sectional view illustrating a step of a dry development method according to an exemplary embodiment. [Figure 10] FIG. 10 is a cross-sectional view illustrating a step in a dry development method according to an exemplary embodiment. [Figure 11] FIG. 11 is a schematic diagram of a dry development apparatus according to another exemplary embodiment. [Figure 12] FIG. 12 is a schematic diagram of a dry development apparatus according to another exemplary embodiment. [Figure 13] FIG. 13 is a schematic diagram of a substrate support according to another exemplary embodiment. [Figure 14] FIG. 14 is a flowchart of a dry development method according to another exemplary embodiment. [Figure 15] FIG. 15 is a diagram illustrating an example of control of the flow rates of the first process gas and the second process gas. [Figure 16] FIG. 16 is a diagram showing another example of control of the flow rates of the first process gas and the second process gas. [Figure 17] FIG. 17 is a flowchart of a dry development method according to another exemplary embodiment. [Figure 18] FIG. 18 is a schematic diagram of a substrate processing system according to one exemplary embodiment. [Figure 19] FIG. 19 is a flowchart of a substrate processing method according to one exemplary embodiment. [Figure 20] FIG. 20 is a graph showing an example of the results of the first experiment. [Figure 21] FIG. 21 is a graph showing an example of the results of the second experiment. [Figure 22] FIG. 22 is a graph showing an example of the results of the third experiment. [Figure 23] FIG. 23 is a table showing an example of the results of the fourth experiment. DETAILED DESCRIPTION OF THE INVENTION

[0008] Various exemplary embodiments will be described in detail below with reference to the drawings, in which the same or equivalent parts are designated by the same reference numerals.

[0009] 1 is a schematic diagram of a dry developing apparatus according to an exemplary embodiment. In the exemplary embodiment, a thermal processing system includes a thermal processing apparatus 100 and a control unit 200. The thermal processing system is an example of a dry developing system. The thermal processing apparatus 100 is an example of a dry developing apparatus.

[0010] The heat treatment apparatus 100 has a process chamber 102 (chamber) that is configured to be airtight. The process chamber 102 is, for example, an airtight cylindrical container, and is configured so that the atmosphere inside can be controlled. A side wall heater 104 is provided on the side wall of the process chamber 102. A ceiling heater 130 is provided on the ceiling wall (top plate) of the process chamber 102. A ceiling surface 140 of the ceiling wall (top plate) of the process chamber 102 is formed as, for example, a horizontal, flat surface. The temperature of the ceiling surface 140 is controlled by the ceiling heater 130.

[0011] A substrate support 121 is provided at the lower side of the processing chamber 102. The substrate support 121 constitutes a mounting portion on which a substrate W is mounted. The substrate support 121 may have, for example, a circular surface (top surface) or a horizontally formed surface (top surface). The substrate W is mounted on the surface of the substrate support 121. A stage heater 120 is embedded in the substrate support 121. This stage heater 120 can heat the substrate W mounted on the substrate support 121. A ring assembly 125 may be disposed on the substrate support 121 to surround the substrate W. The ring assembly 125 may include one or more annular members. The provision of the ring assembly 125 can improve temperature controllability in the outer peripheral region of the substrate W. The ring assembly 125 may be made of an inorganic material or an organic material depending on the desired heat treatment.

[0012] The substrate support 121 is supported by the processing chamber 102 by support columns 122 provided on the bottom surface of the processing chamber 102. A plurality of lift pins 123 that, for example, vertically move up and down are provided on the outer circumferential sides of the support columns 122. The plurality of lift pins 123 are inserted into a plurality of through holes that are provided at intervals in the circumferential direction of the substrate support 121. The lifting and lowering operation of the lift pins 123 is controlled by a lifting mechanism 124. When the lift pins 123 protrude from the surface of the substrate support 121, the substrate W is transferred between a transport mechanism (not shown) and the substrate support 121.

[0013] An exhaust port 131 having an opening is provided in the sidewall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump, a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. The pressure inside the processing chamber 102 is adjusted by adjusting the exhaust flow rate, etc., using the exhaust mechanism 132. A transfer port for a substrate W (not shown) that can be opened and closed is formed in the sidewall of the processing chamber 102 at a position different from the position of the exhaust port 131.

[0014] A gas nozzle 141 is provided on the sidewall of the processing chamber 102 at a position different from the exhaust port 131 and the transfer port for the substrate W. The gas nozzle 141 supplies processing gas into the processing chamber 102. The gas nozzle 141 is provided on the sidewall of the processing chamber 102 on the opposite side from the exhaust port 131 when viewed from the center of the substrate support 121.

[0015] The gas nozzle 141 is formed in a rod shape that protrudes from the sidewall of the processing chamber 102 toward the center of the processing chamber 102. The tip of the gas nozzle 141 extends, for example, horizontally from the sidewall of the processing chamber 102. The processing gas is discharged into the processing chamber 102 from a discharge port provided at the tip of the gas nozzle 141. The discharged processing gas flows in the direction of arrow AR1 shown in FIG. 1 and is exhausted from the exhaust port 131. The tip of the gas nozzle 141 may extend obliquely downward toward the substrate W, or may extend obliquely upward toward a ceiling surface 140 of the processing chamber 102.

[0016] The gas nozzle 141 may be provided, for example, in the ceiling wall of the processing chamber 102. The exhaust port 131 may be provided in the bottom surface of the processing chamber 102.

[0017] The heat treatment apparatus 100 has a gas supply pipe 152 connected to a gas nozzle 141 from the outside of the processing chamber 102. A piping heater 160 for heating the inside of the gas supply pipe 152 is provided around the gas supply pipe 152. The gas supply pipe 152 is connected to a gas supply unit 170. The gas supply unit 170 includes at least one gas source and at least one flow rate controller. The gas supply unit may include a vaporizer that vaporizes the gas source in a liquid state.

[0018] The control unit 200 processes computer-executable instructions that cause the heat treatment apparatus 100 to perform the various steps described in this disclosure. The control unit 200 may be configured to control each element of the heat treatment apparatus 100 to perform the various steps described herein. In one embodiment, part or all of the control unit 200 may be included in the heat treatment apparatus 100. The control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3. The control unit 200 is implemented, for example, by the computer 200a. The processing unit 200a1 may be configured to read a program from the storage unit 200a2 and execute the read program to perform various control operations. This program may be stored in the storage unit 200a2 in advance or may be acquired via a medium when needed. The acquired program is stored in the storage unit 200a2 and read from the storage unit 200a2 by the processing unit 200a1 and executed. The medium may be various storage media readable by the computer 200a or a communication line connected to the communication interface 200a3. The processing unit 200a1 may be a CPU (Central Processing Unit). The storage unit 200a2 may include a RAM (Random Access Memory), a ROM (Read Only Memory), an HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 may communicate with the heat treatment device 100 via a communication line such as a LAN (Local Area Network).

[0019] FIG. 2 is a schematic diagram illustrating a dry developing apparatus according to another exemplary embodiment. In this embodiment, a plasma processing system includes a plasma processing apparatus 1 and a controller 2. The plasma processing system is an example of a dry developing system, and the plasma processing apparatus 1 is an example of a dry developing apparatus. The plasma processing apparatus 1 includes a plasma processing chamber (hereinafter simply referred to as a "processing chamber") 10, a substrate support 11, and a plasma generation unit 12. The plasma processing chamber 10 has a plasma processing space. The plasma processing chamber 10 also has at least one gas supply port for supplying at least one processing gas to the plasma processing space and at least one gas exhaust port for exhausting gas from the plasma processing space. The gas supply port is connected to a gas supply unit 20 (described later), and the gas exhaust port is connected to an exhaust system 40 (described later). The substrate support 11 is disposed in the plasma processing space and has a substrate support surface for supporting a substrate W.

[0020] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be capacitively coupled plasma (CCP), inductively coupled plasma (ICP), electron-cyclotron-resonance plasma (ECR plasma), helicon wave plasma (HWP), or surface wave plasma (SWP). Various types of plasma generating units may be used, including alternating current (AC) plasma generating units and direct current (DC) plasma generating units. In one embodiment, the AC signal (AC power) used in the AC plasma generating unit has a frequency in the range of 100 kHz to 10 GHz. Therefore, the AC signal includes a radio frequency (RF) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0021] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various steps described in this disclosure. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to perform the various steps described herein. In one embodiment, some or all of the control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 is realized by, for example, a computer 2a. The control unit 2 may include a processing unit 2a1, a memory unit 2a2, and a communication interface 2a3. Each component of the control unit 2 may be the same as each component of the control unit 200 (see FIG. 1) described above.

[0022] The following describes a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1. Fig. 3 is a diagram schematically showing a dry developing apparatus according to another exemplary embodiment.

[0023] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply 20, a power supply 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support 11 and a gas inlet. The gas inlet is configured to introduce at least one process gas into the plasma processing chamber 10. The gas inlet includes a showerhead 13. The substrate support 11 is disposed within the plasma processing chamber 10. The showerhead 13 is disposed above the substrate support 11. In one embodiment, the showerhead 13 forms at least a portion of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the showerhead 13, a sidewall 10a of the plasma processing chamber 10, and the substrate support 11. The plasma processing chamber 10 is grounded. The showerhead 13 and the substrate support 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0024] The substrate support 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central region 111a for supporting a substrate W and an annular region 111b for supporting the ring assembly 112. A wafer is an example of a substrate W. The annular region 111b of the main body 111 surrounds the central region 111a of the main body 111 in a plan view. The substrate W is disposed on the central region 111a of the main body 111, and the ring assembly 112 is disposed on the annular region 111b of the main body 111 so as to surround the substrate W on the central region 111a of the main body 111. Therefore, the central region 111a is also called a substrate support surface for supporting the substrate W, and the annular region 111b is also called a ring support surface for supporting the ring assembly 112.

[0025] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive member. The conductive member of the base 1110 may function as a lower electrode. The electrostatic chuck 1111 is disposed on the base 1110. The electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within the ceramic member 1111a. The ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that the annular region 111b may also be provided by another member surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member. In this case, the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating member, or may be disposed on both the electrostatic chuck 1111 and the annular insulating member. Furthermore, at least one RF / DC electrode coupled to an RF power supply 31 and / or a DC power supply 32, which will be described later, may be disposed within the ceramic member 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or a DC signal, which will be described later, is supplied to the at least one RF / DC electrode, the RF / DC electrode is also called a bias electrode. Note that the conductive member of the base 1110 and the at least one RF / DC electrode may function as multiple lower electrodes. Alternatively, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support 11 includes at least one lower electrode.

[0026] The ring assembly 112 includes one or more annular members. In one embodiment, the one or more annular members include one or more edge rings and at least one cover ring. The edge rings are formed of a conductive or insulating material, and the cover rings are formed of an insulating material.

[0027] The substrate support 11 may include a temperature adjustment module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature adjustment module may include a heater, a heat transfer medium, a flow passage 1110a, or a combination thereof. A heat transfer fluid, such as brine or a gas, flows through the flow passage 1110a. In one embodiment, the flow passage 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111. The substrate support 11 may also include a heat transfer gas supply configured to supply a heat transfer gas to a gap between the backside of the substrate W and the central region 111a.

[0028] The showerhead 13 is configured to introduce at least one processing gas from the gas supply unit 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and multiple gas inlets 13c. The processing gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the multiple gas inlets 13c. The showerhead 13 also includes at least one upper electrode. In addition to the showerhead 13, the gas introduction unit may also include one or more side gas injectors (SGIs) attached to one or more openings formed in the sidewall 10a.

[0029] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one process gas from a corresponding gas source 21 to the showerhead 13 via a corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Additionally, the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of the at least one process gas.

[0030] The power supply 30 includes an RF power supply 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The RF power supply 31 is configured to supply at least one RF signal (RF power) to at least one lower electrode and / or at least one upper electrode. This generates a plasma from at least one processing gas supplied to the plasma processing space 10s. Therefore, the RF power supply 31 can function as at least a part of the plasma generation unit 12. Furthermore, by supplying a bias RF signal to the at least one lower electrode, a bias potential is generated on the substrate W, and ion components in the formed plasma can be attracted to the substrate W.

[0031] In one embodiment, the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b. The first RF generating unit 31a is coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit and is configured to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generating unit 31a may be configured to generate multiple source RF signals having different frequencies. The generated one or more source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0032] The second RF generating unit 31b is coupled to at least one lower electrode via at least one impedance matching circuit and configured to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF generating unit 31b may be configured to generate multiple bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. In various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0033] The power supply 30 may include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generator 32a and a second DC generator 32b. In one embodiment, the first DC generator 32a is connected to at least one lower electrode and configured to generate a first DC signal. The generated first DC signal is applied to the at least one lower electrode. In one embodiment, the second DC generator 32b is connected to at least one upper electrode and configured to generate a second DC signal. The generated second DC signal is applied to the at least one upper electrode.

[0034] In various embodiments, the first and second DC signals may be pulsed. In this case, a sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulses may have a rectangular, trapezoidal, triangular, or combination thereof. In one embodiment, a waveform generator for generating a sequence of voltage pulses from the DC signal is connected between the first DC generator 32a and at least one lower electrode. Thus, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. When the second DC generator 32b and the waveform generator constitute a voltage pulse generator, the voltage pulse generator is connected to at least one upper electrode. The voltage pulses may have either positive or negative polarity. Furthermore, the sequence of voltage pulses may include one or more positive voltage pulses and one or more negative voltage pulses within one period. The first and second DC generating units 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generating unit 32a may be provided instead of the second RF generating unit 31b.

[0035] The exhaust system 40 may be connected to, for example, a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure regulating valve regulates the pressure in the plasma processing space 10s. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0036] [First embodiment] FIG. 4 is a flowchart of a dry development method (hereinafter referred to as "method MT1") according to one example embodiment. As shown in FIG. 4, method MT1 includes step ST11 of providing a substrate W, step ST12 of supplying a first process gas, and step ST13 of supplying a second process gas. Method MT1 may include step ST14 of determining whether a stop condition is satisfied after step ST13. Method MT1 may include step ST15 of purging the interior space of chamber 102 between steps ST12 and ST13. Method MT1 may include step ST16 of purging the interior space of chamber 102 between steps ST13 and ST14. At least one of steps ST15 and ST16 may be performed. Method MT1 does not necessarily have to include steps ST15 and ST16.

[0037] The method MT1 may be performed using any one of the substrate processing systems described above (see FIGS. 1 to 3), or may be performed using two or more of these substrate processing systems. For example, the method MT1 may be performed by a heat treatment system (see FIG. 1). The following describes an example in which the control unit 200 controls each unit of the heat treatment apparatus 100 to perform the method MT1 on the substrate W.

[0038] (Process ST11: Providing the substrate) First, in step ST11, a substrate W is provided in the processing chamber 102 of the thermal processing apparatus 100. The substrate W is provided on the substrate support 121, for example, by lowering the lift pins 123. After the substrate W is placed on the substrate support 121, the temperature of the substrate support 121 is adjusted to a set temperature. The temperature adjustment of the substrate support 121 may be performed by controlling the output of one or more of the sidewall heater 104, the stage heater 120, the ceiling heater 130, and the piping heater 160. In method MT1, the temperature of the substrate support 121 may be adjusted to the set temperature before step ST11. That is, the substrate W may be provided on the substrate support 121 after the temperature of the substrate support 121 is adjusted to the set temperature.

[0039] 5 is a cross-sectional view of an example substrate W to which method MT1 can be applied. The substrate W includes a liner UF and a metal-containing resist MF formed on the liner UF. The substrate W may be used in the manufacture of semiconductor devices. The semiconductor devices include, for example, memory devices such as DRAMs and 3D-NAND flash memories, and logic devices.

[0040] The metal-containing resist MF may contain at least one selected from the group consisting of tin (Sn), hafnium (Hf), and titanium (Ti). The metal-containing resist MF may contain, for example, at least one selected from the group consisting of tin oxide, hafnium oxide, and titanium oxide, or may contain an organic substance.

[0041] The metal-containing resist MF may be an EUV resist. As shown in Figure 5, the metal-containing resist MF has an exposed first region MF1 and an unexposed second region MF2. The first region MF1 may be an exposed region that is exposed to EUV. The second region MF2 may be an unexposed region that is not exposed to EUV.

[0042] The underlayer UF may be formed on a silicon wafer and may be a carbon-containing film, a dielectric film, a metal film, a semiconductor film, or a laminated film thereof.

[0043] 6 and 7 are cross-sectional views of another example of a substrate W to which the method MT1 can be applied. As shown in Fig. 6, the base film UF may be composed of a first film UF1, a second film UF2, and a third film UF3. Also, as shown in Fig. 7, the base film UF may be composed of a second film UF2 and a third film UF3.

[0044] The first film UF1 is, for example, a spin-on-glass (SOG) film, a SiC film, a SiON film, a Si-containing antireflective coating (SiARC), or a carbon-containing 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 formed by stacking multiple types of silicon-containing films. For example, the third film UF3 may be formed by alternately stacking silicon oxide films and silicon nitride films. The third film UF3 may be formed by alternately stacking silicon oxide films and polycrystalline silicon films. The third film UF3 may be a stacked film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. The third film UF3 may be formed by stacking a silicon oxide film and a 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.

[0045] In one embodiment, the substrate W is formed as follows. First, a metal-containing photoresist film is formed on an underlayer film that has been subjected to adhesion treatment, etc. The film formation may be performed by a dry process, a wet process such as a solution coating method, or both a dry process and a wet process. The underlayer film may be subjected to a surface modification process before the photoresist film is formed. After the film formation, the wafer is subjected to a heat treatment, i.e., a post-apply bake (PAB). An additional heat treatment may be performed after the pre-baking. After the heat treatment, the wafer is transferred to an exposure tool, and the photoresist film is irradiated with EUV light through an exposure mask (reticle). This forms a substrate W having an underlayer film UF and a metal-containing resist MF having an exposed first region MF1 and an unexposed second region MF2. The first region MF1 corresponds to an opening formed in the exposure mask (reticle). The second region MF2 corresponds to a pattern formed in the exposure mask (reticle). EUV has a wavelength in the range of 10 nm to 20 nm, for example. EUV may have a wavelength in the range of 11 nm to 14 nm, and in one example has a wavelength of 13.5 nm. The exposed wafer is transferred from the exposure tool to a heat treatment tool under controlled atmosphere and subjected to a heat treatment, i.e., a post-exposure bake (PEB). The exposed wafer may be further subjected to a heat treatment after the PEB.

[0046] (Step ST12: Supply of First Processing Gas) In the following description, the substrate W shown in FIG. 5 is assumed to be processed. FIGS. 8 to 10 are cross-sectional views showing steps of a dry development method according to an exemplary embodiment. FIG. 8 is a cross-sectional view of the substrate W at step ST12. In step ST12, a first process gas containing a fluorine-containing gas is supplied into the processing chamber 10, thereby forming a metal fluoride layer MF21 on the surface of the second region MF2, as shown in FIG. 8. In step ST12, fluorine contained in the fluorine-containing gas reacts with a metal (e.g., tin) present on the surface of the second region MF2 to form the metal fluoride layer MF21 (e.g., a tin fluoride (SnF) layer). In the example of FIG. 8, the metal fluoride layer MF21 may be formed without generating plasma. At the end of step ST12, the supply of the first process gas may be stopped.

[0047] The fluorine-containing gas may include at least one selected from the group consisting of hydrogen fluoride gas (HF gas) and xenon fluoride gas (e.g., XeF2 gas). The first process gas may include an inert gas. The inert gas may include a noble gas. The inert gas may include at least one selected from the group consisting of nitrogen gas (N2 gas), argon gas (Ar gas), xenon gas (Xe gas), and krypton gas (Kr gas).

[0048] In step ST12, the partial pressure of the fluorine-containing gas supplied into the processing chamber 10 may be controlled. The partial pressure of the fluorine-containing gas may be 13.3 Pa or more. The partial pressure of the fluorine-containing gas may be 13.3 kPa or less. The partial pressure of the fluorine-containing gas may be 13.3 Pa or more and 13.3 kPa or less. The partial pressure of the fluorine-containing gas may be 0.1 Torr or more. The partial pressure of the fluorine-containing gas may be 100 Torr or less. The partial pressure of the fluorine-containing gas may be 0.1 Torr or more and 100 Torr or less.

[0049] In step ST12, the substrate support 121 may be heated. Step ST12 may be performed in a state in which the temperature of the substrate support 121 is set to a first temperature. The first temperature may be 0°C or higher. The first temperature may be 30°C or higher. The first temperature may be 100°C or higher. The first temperature may be 300°C or lower. The first temperature may be 30°C or higher and 300°C or lower.

[0050] (Process ST15: Purge) After step ST12, step ST15 may be performed to purge the internal space of the chamber 102. In step ST15, for example, an inert gas may be supplied into the chamber 102, and gases and the like may be discharged from the chamber 102. The inert gas may include at least one gas selected from the group consisting of nitrogen gas and argon gas.

[0051] (Step ST13: Supply of second processing gas) FIG. 9 is a cross-sectional view of the substrate W in step ST13. After step ST12, in step ST13, a second process gas containing a chlorine-containing gas is supplied into the process chamber 10 to remove the metal fluoride layer MF21, as shown in FIG. 9. In step ST13, the metal fluoride layer MF21 can be selectively removed relative to the first region MF1 through a reaction between the chlorine-containing gas and the metal fluoride layer MF21. In step ST13, a volatile metal chloride can be generated through an exchange reaction between chlorine in the chlorine-containing gas and fluorine in the metal fluoride layer MF21. By performing step ST13, a recess RE can be formed in the substrate W, as shown in FIG. 9. At the end of step ST13, the supply of the second process gas can be stopped.

[0052] The chlorine-containing gas may include at least one selected from the group consisting of silicon tetrachloride gas (SiCl4 gas), titanium tetrachloride gas (TiCl4 gas), dimethylaluminum chloride gas (DMAC gas), thionyl chloride gas (SOCl2 gas), and acetyl chloride gas (CH3COCl gas). The second process gas may include an inert gas. The inert gas may include a noble gas. The inert gas may include at least one selected from the group consisting of nitrogen gas (N2 gas), argon gas (Ar gas), xenon gas (Xe gas), and krypton gas (Kr gas).

[0053] The pressure in the processing chamber 10 in step ST13 may be lower than the pressure in the processing chamber in step ST12. In step ST13, the partial pressure of the chlorine-containing gas supplied into the processing chamber 10 may be controlled. The partial pressure of the chlorine-containing gas may be 13.3 Pa or more. The partial pressure of the chlorine-containing gas may be 13.3 kPa or less. The partial pressure of the chlorine-containing gas may be 13.3 Pa or more and 13.3 kPa or less. The partial pressure of the chlorine-containing gas may be 0.1 Torr or more. The partial pressure of the fluorine-containing gas may be 100 Torr or less. The partial pressure of the chlorine-containing gas may be 0.1 Torr or more and 100 Torr or less.

[0054] In step ST13, the substrate support 121 may be heated. Step ST13 may be performed in a state in which the temperature of the substrate support 121 is set to a second temperature. The second temperature may be the same as the first temperature, or may be higher than the first temperature. The second temperature may be 30°C or higher, or 100°C or higher. The second temperature may be 300°C or lower, or 200°C or lower. The second temperature may be 30°C or higher and 300°C or lower.

[0055] (Process ST16: Purge) After step ST13, a step of purging the internal space of the chamber 102 may be performed in step ST16. In step ST16, for example, an inert gas may be supplied into the chamber 102, and gases and the like may be discharged from the chamber 102. The inert gas may include at least one selected from the group consisting of nitrogen gas and argon gas.

[0056] Step ST12 and step ST13 may be repeated in this order. That is, method MT1 may include a step of repeating step ST12 and step ST13 (corresponding to step ST14). In the step of repeating step ST12 and step ST13, at least one of step ST15 and step ST16 may be repeated. The step of repeating step ST12 and step ST13 may be repeated a predetermined number of times. The step of repeating step ST12 and step ST13 may be repeated until the recess RE reaches the underlayer film UF (until the underlayer film UF is exposed). The step of performing step ST12 and step ST13 once each may be considered as one cycle. In this case, the thickness of the second region MF2 removed per cycle in the direction from the metal-containing resist MF toward the underlayer film UF may be 5 nm or more and 20 nm or less.

[0057] The step of repeating step ST12 and step ST13 may include changing at least one selected from the group consisting of the pressure in the chamber 102, the temperature of the substrate support member 121, the processing time of step ST12, and the processing time of step ST13, in accordance with the aspect ratio of the recess RE formed in step ST13. For example, the step of repeating step ST12 and step ST13 may include performing at least one of decreasing the pressure in the chamber 102, decreasing the temperature of the substrate support member 121, shortening the processing time of step ST12, and shortening the processing time of step ST13, in accordance with an increase in the aspect ratio of the recess RE formed in step ST13.

[0058] In the method MT1, the pressure in the chamber 102, the temperature of the substrate support member 121, the processing time of step ST12, and the processing time of step ST13 (hereinafter, sometimes referred to as each parameter) may be adjusted according to the aspect ratio of the recessed portion RE each time step ST12 and step ST13 are repeated. Each parameter may be adjusted based on the absolute value of the aspect ratio, or may be adjusted based on the increase in the aspect ratio. For example, in the method MT1, each parameter may be decreased by several percent to several tens of percent according to the increase in the aspect ratio of the recessed portion RE each time step ST12 and step ST13 are repeated. A limit may be placed on the number of times each parameter is adjusted.

[0059] For example, a table indicating the relationship between the aspect ratio of the recessed portion RE and each parameter may be stored in the storage unit 200a2 of the control unit 200. The control unit 200 may adjust each parameter based on the table stored in the storage unit 200a2.

[0060] (Process ST14: Judgment) The method MT1 may include step ST14, which determines whether a stop condition is satisfied. The stop condition may be satisfied when the removal amount (depth of the recess RE) of the second region MF2 reaches a threshold value. The stop condition may be satisfied when the base film UF is exposed. The stop condition may be satisfied when the total processing time of steps ST12 and ST13 reaches a threshold value. The stop condition may be satisfied when the number of repetitions of steps ST12 and ST13 reaches a threshold value. If the stop condition is not satisfied in step ST14 (step ST14: NO), steps ST12 and ST13 may be repeated again. In this case, in the method MT1, the processing conditions may be changed from those in the previous cycle to perform the next cycle. In the method MT1, for example, the partial pressure of the fluorine-containing gas and the partial pressure of the chlorine-containing gas may be changed. In the method MT1, for example, the temperature of the substrate support 121 may be changed, or the type of noble gas may be changed. In the method MT1, the above-mentioned changes may be combined as appropriate. On the other hand, if the stopping condition is satisfied in step ST14 (step ST14: YES), the method MT1 may end.

[0061] According to the method MT1, the second region MF2 can be selectively removed relative to the first region MF1. Therefore, the metal-containing resist can be appropriately developed. Specifically, in the method MT1, the first region MF1 is removed at a first rate, while the second region MF2 can be removed at a second rate that is greater than the first rate. The first rate is, for example, 1 nm / cycle or less. The second rate is, for example, 2 nm / cycle or more and 10 nm / cycle or less. Therefore, the second region MF2 can be removed with a high selectivity (the ratio of the rate at which the second region MF2 is removed to the rate at which the first region MF1 is removed) relative to the first region MF1.

[0062] The mechanism by which the second region MF2 can be selectively removed relative to the first region MF1 is presumed to be as follows, but is not limited to this. Both the first region MF1 and the second region MF2 contain, for example, bonds between tin and oxygen (Sn—O bonds). When the first region MF1 and the second region MF2 are exposed to a fluorine-containing gas, the Sn—O bonds are replaced with Sn—F bonds. The first region MF1 contains a larger number of Sn—O bonds than the second region MF2. In other words, the density of Sn—O bonds per unit volume is relatively high in the first region MF1. Therefore, the replacement of Sn—F bonds by the fluorine-containing gas is more likely to occur to a deeper position in the second region MF2 than in the first region MF1. Furthermore, the number of organic ligands contained in the second region MF2 is greater than the number of organic ligands contained in the first region MF1. Therefore, the second region MF2 is more likely to volatilize than the first region MF1.

[0063] Furthermore, in method MT1, the thickness of the metal fluoride layer MF21 formed in step ST12 saturates at a certain point. Therefore, the depth of the recesses RE formed in step ST13 (the amount of removal of the second regions MF2) can be controlled. Therefore, method MT1 can obtain high in-plane uniformity in the depth of the recesses RE. In other words, the difference between the depth of the recesses RE at the center of the substrate W and the depth of the recesses RE at the periphery of the substrate W can be reduced.

[0064] When plasma is not generated in step ST12, damage to the substrate W or the substrate support part 121 can be suppressed more effectively than when plasma is used.

[0065] In step ST12, when the first temperature of the substrate support 121 is 30° C. or higher, the reaction between the second region MF2 and the fluorine-containing gas is promoted.

[0066] The second temperature of the substrate support 121 in step ST13 may be higher than the first temperature of the substrate support 121 in step ST12. In this case, the reaction between the metal fluoride layer MF21 and the chlorine-containing gas is promoted, thereby promoting removal of the metal fluoride layer MF21. For example, if the metal fluoride layer MF21 is an SnF layer, the reaction between the chlorine-containing gas and SnF may exchange F in SnF for Cl. As a result, highly volatile SnCl may be produced. Setting the temperature of the substrate support 121 to the second temperature promotes the reaction between the chlorine-containing gas and SnF and the volatilization of SnCl.

[0067] When the method MT1 includes repeating the steps ST12 and ST13, the thickness of the second region MF2 removed in the direction from the metal-containing resist MF toward the undercoat film UF can be increased.

[0068] The process of repeating step ST12 and step ST13 may include performing at least one of reducing the pressure in the chamber 102, reducing the temperature of the substrate support 121, shortening the processing time of step ST12, and shortening the processing time of step ST13 in response to an increase in the aspect ratio of the recess RE formed in step ST13. The recess RE of the metal-containing resist MF tends to have an inverted tapered shape, with the width increasing toward the bottom (toward the underlayer UF). In contrast, the progress of dry development can be suppressed by, for example, reducing the pressure in the chamber 102 in response to an increase in the aspect ratio of the recess RE. As a result, the sidewall of the recess RE is less likely to be scraped off, allowing the sidewall shape of the recess RE after development to approach verticality.

[0069] [Second embodiment] As the heat treatment system, a heat treatment apparatus 100a shown in FIGS. 11 and 12 may be used instead of the heat treatment apparatus 100 shown in FIG. 1. FIGS. 11 and 12 are diagrams schematically illustrating a dry developing apparatus according to another exemplary embodiment. FIG. 11 is a schematic cross-sectional view illustrating an example configuration of the heat treatment apparatus 100a. FIG. 12 is a schematic plan view illustrating an example configuration of the heat treatment apparatus 100a. The heat treatment apparatus 100a includes a shower head 141a provided on the ceiling of the processing chamber 102 and multiple gas nozzles 141b provided on the sidewall of the processing chamber 102. The shower head 141a may be disposed opposite the substrate support 121. The multiple gas nozzles 141b may be disposed, for example, at equal intervals along the circumferential direction on the sidewall of the processing chamber 102. The multiple gas nozzles 141b may include a first gas nozzle 141b1 and a second gas nozzle 141b2. The first gas nozzle 141b1 and the second gas nozzle 141b2 may be arranged alternately. The types of gas supplied into the processing chamber 102 from the shower head 141a, the gas nozzles 141b1, and the gas nozzles 141b2 may be the same or different. Gas from the shower head 141a is supplied into the processing chamber 102 in the direction of arrow AR2 shown in FIG. 11. Gas from the gas nozzle 141b1 is supplied into the processing chamber 102 in the direction of arrow AR3 shown in FIGS. 11 and 12. Gas from the gas nozzle 141b2 is supplied into the processing chamber 102 in the direction of arrow AR4 shown in FIGS. 11 and 12. The flow rates of gas supplied into the processing chamber 102 from the shower head 141a, the gas nozzles 141b1, and the gas nozzles 141b2 may be the same or different. Heaters may be provided on sidewalls of the substrate support 121 and the processing chamber 102. A gas exhaust port may be located at the bottom of the processing chamber 102 .

[0070] According to the heat treatment apparatus 100a, the gas density in the processing chamber 102 can be easily controlled, and the in-plane uniformity in the development of the metal-containing resist MF can be improved.

[0071] [Third embodiment] As the substrate support, a substrate support 121a shown in FIG. 13 may be used instead of the substrate support 121 shown in FIG. 1. FIG. 13 is a diagram schematically illustrating a substrate support 121a according to another exemplary embodiment. The substrate support 121a shown in FIG. 13 has multiple zones, each of which is provided with a heater electrode. In the example shown in FIG. 13, the substrate support 121a has zones Z1 to Z14. The heater electrodes of each of the zones Z1 to Z14 are configured to be able to receive power independently. In other words, the substrate support 121a is configured to be able to control the temperature independently for each zone. Therefore, the substrate support 121a can improve the in-plane uniformity in the development of the metal-containing resist MF.

[0072] [Fourth embodiment] The method MT1 may be performed by the plasma processing apparatus 1 shown in FIGS. 2 and 3 instead of the heat processing apparatus 100a. In this case, the metal fluoride layer MF21 may be formed in step ST12 using plasma generated from a first processing gas containing a fluorine-containing gas. By converting the first processing gas containing a fluorine-containing gas into plasma, activated species such as fluorine ions and fluorine radicals can be generated. In the fourth embodiment, the fluorine-containing gas may include at least one selected from the group consisting of hydrogen fluoride gas (HF gas), xenon fluoride gas, fluorocarbon gas, hydrofluorocarbon gas, nitrogen fluoride gas, and sulfur fluoride gas. The fluorocarbon gas may include at least one selected from the group consisting of C4F6 gas, C4F8 gas, C3F8 gas, and CF4 gas. The hydrofluorocarbon gas may include at least one selected from the group consisting of CHF3 gas and CH2F2 gas. The nitrogen fluoride gas may include NF3 gas. The sulfur fluoride gas may include SF6 gas.

[0073] [Fifth embodiment] In the dry development method according to the fifth embodiment, a precoat may be formed on the sidewall of the processing chamber 102 or on parts inside the processing chamber 102, such as the substrate support 121, before development begins. The precoat may be formed by atomic layer deposition (ALD), chemical vapor deposition (CVD), or the like. A gas capable of forming a film resistant to a processing gas containing carboxylic acid may be selected as the gas for forming the precoat. For example, a silicon-containing gas may be used as the gas for forming the precoat. The silicon-containing gas may contain at least one selected from the group consisting of aminosilane and SiCl4. In this case, a silicon oxide film may be formed as the precoat on the sidewall of the processing chamber 102 or on the parts inside the processing chamber 102. This can prevent corrosion of the sidewall of the processing chamber 102 or the parts inside the processing chamber 102 by the processing gas.

[0074] In the dry development method according to the fifth embodiment, instead of or in addition to the pre-coating, the sidewalls and internal parts of the processing chamber 102 may be made of a material that is resistant to processing gases containing carboxylic acids, etc.

[0075] In the dry development method according to the fifth embodiment, the inside of the processing chamber 102 may be cleaned after development. In this case, the processing chamber 102 and its internal components may be heated, and then a cleaning gas may be supplied into the processing chamber 102. The cleaning gas may be a gas containing hydrogen halide. The hydrogen halide gas may include at least one gas selected from the group consisting of hydrogen bromide gas (HBr gas) and hydrogen fluoride gas. Cleaning may be performed by thermal atomic layer etching (hereinafter also referred to as "thermal ALE"). This allows metal oxides adhering to the sidewalls of the processing chamber 102 and its internal components during development to be removed.

[0076] [Sixth embodiment] In the dry development method according to the sixth embodiment, the base film UF may be etched using the metal-containing resist MF developed by the method MT1 as a mask. The etching conditions for the base film UF may be selected based on the film type of the base film UF, etc. The etching of the base film UF may be performed by the plasma processing apparatus 1 shown in FIG.

[0077] [Seventh embodiment] 14 is a flowchart of a dry development method (hereinafter referred to as "method MT2") according to another exemplary embodiment. The method MT2 includes step ST21 of providing a substrate W and step ST22 of supplying a processing gas. The method MT2 may include step ST23 of determining whether a stop condition is satisfied after step ST22. The substrate W may be the same as the substrate W of the first embodiment. The method MT2 develops the metal-containing resist MF.

[0078] In method MT2, in step ST22, a process gas containing a fluorine-containing gas and a chlorine-containing gas is supplied into the process chamber 102 to remove the second region MF2. In step ST22, a mixed gas containing a fluorine-containing gas and a chlorine-containing gas may be supplied as the process gas. That is, in step ST22, a fluorine-containing gas and a chlorine-containing gas may be supplied simultaneously. In this case, the step of forming a metal fluoride layer MF21 on the surface of the second region MF2 using the fluorine-containing gas and the step of removing the metal fluoride layer MF21 using the chlorine-containing gas may be performed simultaneously. The types of gases contained in the fluorine-containing gas and the chlorine-containing gas may be the same as those in method MT1.

[0079] In the method MT2, the ratio (F2 / F1) of the flow rate F2 of the chlorine-containing gas to the flow rate F1 of the fluorine-containing gas may be adjusted as needed. F2 / F1 may be changed during the execution of step ST22. In one embodiment, F2 / F1 may be changed as needed depending on the processing time of step ST22 or the aspect ratio of the recess RE formed in step ST22. For example, as the aspect ratio of the recess RE increases, the flow rates of the fluorine-containing gas and the chlorine-containing gas may be adjusted so that F2 / F1 increases, or the flow rates of the fluorine-containing gas and the chlorine-containing gas may be adjusted so that F2 / F1 decreases.

[0080] Step ST22 may include reducing the pressure in the chamber 102 in response to an increase in the aspect ratio of the recess RE. Step ST22 may include changing at least one selected from the group consisting of the pressure in the chamber 102, the temperature of the substrate support member 121, the processing time of step ST12, and the processing time of step ST13 in response to an increase in the aspect ratio of the recess RE. For example, step ST22 may include performing at least one of reducing the pressure in the chamber 102, reducing the temperature of the substrate support member 121, shortening the processing time of step ST12, and shortening the processing time of step ST13 in response to an increase in the aspect ratio of the recess RE.

[0081] Each parameter may be adjusted based on the absolute value of the aspect ratio or based on the increase in the aspect ratio. For example, in step ST22, the pressure in the chamber 102 may be reduced in accordance with the increase in the aspect ratio of the recess RE.

[0082] In method MT2, the flow rates of the fluorine-containing gas and the chlorine-containing gas may be adjusted so that F2 / F1 varies periodically. Step ST22 may include a first period and a second period following the first period. In this case, F2 / F1 in the first period may be larger or smaller than F2 / F1 in the second period.

[0083] In step ST22, it is possible to control the temperature of the substrate support 121. An example of the temperature of the substrate support 121 in step ST22 may be the same as the example of the temperature of the substrate support 121 in step ST12 or step ST13 of the method MT1.

[0084] The method MT2 may include step ST23, which determines whether a stop condition is satisfied. Step ST23 may be performed in the same manner as step ST14 of the method MT1. The stop condition may be satisfied when the removal amount of the second region MF2 (the depth of the recess RE) reaches a threshold value. The stop condition may be satisfied when the base film UF is exposed. The stop condition may be satisfied when the processing time of step ST22 reaches a threshold value. If the stop condition is not satisfied in step ST23 (step ST23: NO), step ST22 may be repeated. In this case, in the method MT2, the processing conditions may be changed from those of the previous step ST22 to perform the next step ST22. In the method MT2, for example, the partial pressure of the fluorine-containing gas and the partial pressure of the chlorine-containing gas may be changed. In the method MT2, for example, the temperature of the substrate support 121 or the type of noble gas may be changed. In the method MT2, the above-mentioned changes may be combined as appropriate. On the other hand, if the stop condition is satisfied in step ST23 (step ST23: YES), the method MT2 may end.

[0085] [Eighth embodiment] 15 is a diagram illustrating an example of control of the flow rates of the first process gas and the second process gas in method MT1. Repeating step ST12 and step ST13 in method MT1 may include a first period P1 in which step ST12 is performed for a first process time T1 and step ST13 is performed for a second process time T2. Repeating step ST12 and step ST13 may include a second period P2 after the first period P1. In the second period P2, step ST12 is performed for a third process time T3 that is shorter than the first process time T1, and step ST13 is performed for a fourth process time T4 that is shorter than the second process time T2.

[0086] In the example of FIG. 15 , during the first processing time T1, the flow rate of the first processing gas is set to a high level, while the flow rate of the second processing gas is adjusted to a low level. Accordingly, step ST12 proceeds during the first processing time T1. The high-level flow rate may be higher than the low-level flow rate. The low-level flow rate may be 50% or less, or 20% or less, of the high-level flow rate. The low-level flow rate may be zero. During the second processing time T2, the flow rate of the first processing gas is set to a low level, while the flow rate of the second processing gas is adjusted to a high level. Accordingly, step ST13 proceeds during the second processing time T2. During the third processing time T3, the flow rate of the first processing gas is set to a high level, while the flow rate of the second processing gas is adjusted to a low level. Accordingly, step ST12 proceeds during the third processing time T3. During the fourth processing time T4, the flow rate of the first processing gas is set to a low level, while the flow rate of the second processing gas is adjusted to a high level. As a result, step ST13 proceeds during the fourth processing time T4.

[0087] The length of the third processing time T3 may be 80% or less, 50% or less, or 20% or less of the length of the first processing time T1. The length of the fourth processing time T4 may be 80% or less, 50% or less, or 20% or less of the length of the second processing time T2.

[0088] In the method according to the eighth embodiment, the progress of dry development is suppressed as the aspect ratio of the recess RE increases. As a result, the sidewalls of the recess RE are less likely to be scraped, and the sidewall shape of the recess RE after development can be made closer to vertical. Furthermore, when the second period P2 is performed at the end of dry development (when the bottom of the recess RE reaches the underlayer UF during the second period P2), the removal selectivity of the second region MF2 relative to the underlayer UF can be improved.

[0089] [Ninth embodiment] 16 is a diagram illustrating another example of control of the flow rates of the first process gas and the second process gas in the method MT1. In the process of repeating step ST12 and step ST13 of the method MT1, one of the first process gas and the second process gas may be continuously supplied into the chamber 102. The other of the first process gas and the second process gas may be supplied into the chamber 102 at a high flow rate (first gas flow rate) and a low flow rate (second gas flow rate) that is lower than the high flow rate, alternately. For example, the other of the first process gas and the second process gas may be supplied into the chamber 102 intermittently. Alternatively, both the first process gas and the second process gas may be supplied into the chamber 102 at a high flow rate and a low flow rate, alternately.

[0090] 16, step ST12 proceeds during a first processing time T1, and step ST13 proceeds during a second processing time T2 following the first processing time T1. The low-level flow rate may be 50% or less of the high-level flow rate, or may be 20% or less. The low-level flow rate may even be zero.

[0091] 16, during the first processing time T1, the first processing gas is continuously supplied into the chamber 102 at a high flow rate. During the second processing time T2, the second processing gas is supplied into the chamber 102 at a flow rate that alternates between a high flow rate and a low flow rate. This is not a limitation, and during the first processing time T1, the first processing gas may be supplied into the chamber 102 at a flow rate that alternates between a high flow rate and a low flow rate. During the second processing time T2, the second processing gas may be continuously supplied into the chamber 102 at a high flow rate.

[0092] At least one of the first process gas and the second process gas may be pulse-controlled by the control unit 200 so that a high level flow rate and a low level flow rate are alternately supplied. The pulse duty ratio of the pulse control may be 50%. Alternatively, the pulse duty ratio of the pulse control may be 20% or more, or 70% or more.

[0093] In the method according to the ninth embodiment, the amount of gas used can be reduced compared to when both the first process gas and the second process gas are supplied continuously.

[0094] [Tenth embodiment] FIG. 17 is a flowchart of a dry development method (hereinafter referred to as "method MT3") according to another exemplary embodiment. Method MT3 may be performed by the plasma processing apparatus 1 of FIG. 2 or 3. Method MT3 may include steps ST12A and ST12B instead of step ST12 in method MT1. Step ST12B may be performed after or before step ST12A. In step ST12A, a metal fluoride layer MF21 may be formed on the surface of the second region MF2 by supplying a first process gas containing a fluorine-containing gas into the processing chamber 10 without generating plasma (see FIG. 8). In step ST12B, the metal fluoride layer MF21 may be formed using plasma generated from the first process gas containing a fluorine-containing gas. By generating plasma from the first process gas containing a fluorine-containing gas, activated species such as fluorine ions and fluorine radicals can be generated.

[0095] [Example of substrate processing system configuration] 18 is a schematic diagram of a substrate processing system SS according to one example embodiment, which includes a first carrier station CS1, a first processing station PS1, a first interface station IS1, an exposure apparatus EX, a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a controller CT.

[0096] The first carrier station CS1 loads and unloads the first carrier C1 between the substrate processing system SS and an external system. The first carrier station CS1 has a loading stage on which a plurality of first loading plates ST1 are provided. The first carrier C1 is loaded on each of the first loading plates ST1. The first carrier C1 has a housing capable of accommodating a plurality of substrates W therein. The first carrier C1 is loaded on each of the first loading plates ST1 in a state where it accommodates a plurality of substrates W or in an empty state where it does not accommodate any substrates W. The first carrier C1 is, for example, a front-opening unified pod (FOUP).

[0097] The first carrier station CS1 transports substrates W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 is provided with a first transport device HD1 located between the mounting table and the first processing station PS1. The first processing station PS1 is provided with a second transport device HD2. The first transport device HD1 transports substrates W between the first carrier C1 on each first mounting plate ST1 and the second transport device HD2 in the first processing station PS1. 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 the pressure therein between atmospheric pressure and vacuum. "Atmospheric pressure" may be the pressure inside the first transfer device HD1. "Vacuum" may be a pressure lower than atmospheric pressure, for example, a medium vacuum of 0.1 Pa to 100 Pa. The interior of the second transfer device HD2 may be atmospheric pressure or vacuum. The load lock module may, for example, transfer a substrate W from a first transfer device HD1 at atmospheric pressure to a second transfer device HD2 at vacuum. The load lock module may, for example, transfer a substrate W from a second transfer device HD2 at vacuum to the first transfer device HD1 at atmospheric pressure.

[0098] The first processing station PS1 performs various processes on the substrate W. In one embodiment, the first processing station PS1 includes a pre-processing module PM1, a resist film forming module PM2, and a first thermal processing module PM3 (hereinafter collectively referred to as the "first substrate processing module PMa"). A second transfer device HD2 in the first processing station PS1 transfers the substrate W. The second transfer device HD2 transfers the substrate W between the first substrate processing modules PMa. The second transfer device HD2 transfers the substrate W between the first processing station PS1 and the first carrier station CS1, or between the first processing station PS1 and the first interface station IS1.

[0099] The pre-treatment module PM1 performs pre-treatment on the substrate W. In one embodiment, the pre-treatment module PM1 includes a temperature adjustment unit that adjusts the temperature of the substrate W, or a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. In one embodiment, the pre-treatment module PM1 includes a hydrophobic treatment unit that performs a surface modification treatment on the substrate W. Each treatment unit in the pre-treatment module PM1 may be configured to include a heat treatment apparatus 100 (see FIG. 1) and a plasma treatment apparatus 1 (see FIGS. 2 and 3).

[0100] The resist film formation module PM2 forms a resist film on the substrate W. In one embodiment, the resist film formation module PM2 includes a dry coating unit. The dry coating unit forms a resist film on the substrate W using a dry process such as a vapor phase deposition method. The dry coating unit may include a CVD apparatus or an ALD (Atomic Layer Deposition) apparatus that performs chemical vapor deposition to form a resist film on the substrate W. Alternatively, the dry coating unit may include a PVD (Physical Vapor Deposition) apparatus that performs physical vapor deposition to form a resist film. The dry coating unit may be a thermal processing apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0101] In one embodiment, the resist film forming module PM2 includes a wet coating unit that forms a resist film on the substrate W using a wet process such as a solution coating method.

[0102] In one embodiment, the resist film formation module PM2 includes both a wet coating unit and a dry coating unit.

[0103] The first thermal treatment module PM3 thermally treats the substrate W. In one embodiment, the first thermal treatment module PM3 includes one or more of a pre-bake (PAB) unit that heat-treats the substrate W on which a resist film has been formed, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. The multiple thermal treatment devices may be configured by stacking thermal treatment devices. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1). The thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0104] The first interface station IS1 has a third transport apparatus HD3. The third transport apparatus HD3 transports the substrate W between the first processing station PS1 and the exposure apparatus EX. The third transport apparatus HD3 has a housing that accommodates the substrate W. The third transport apparatus HD3 may be configured to be able to control the temperature, humidity, pressure, etc. inside the housing.

[0105] The exposure apparatus EX uses an exposure mask (reticle) to expose a resist film on the substrate W. The exposure apparatus EX may be, for example, an EUV exposure apparatus that uses EUV as a light source.

[0106] The second interface station IS2 has a fourth transport apparatus HD4. The fourth transport apparatus HD4 transports substrates W between the exposure apparatus EX and the second processing station PS2. The fourth transport apparatus HD4 has a housing that accommodates the substrates W. The fourth transport apparatus HD4 may be configured to be able to control the temperature, humidity, pressure, etc. inside the housing.

[0107] The second processing station PS2 performs various processes on the substrate W. In one embodiment, the second processing station PS2 includes a second thermal processing module PM4, a measurement module PM5, a development module PM6, and a third thermal processing module PM7 (hereinafter collectively referred to as the "second substrate processing module PMb"). The second processing station PS2 has a fifth transfer device HD5. The fifth transfer device HD5 transfers the substrate W. The fifth transfer device HD5 transfers the substrate W between the second substrate processing modules PMb. The fifth transfer device HD5 transfers the substrate W between the second processing station PS2 and the second carrier station CS2 or between the second processing station PS2 and the second interface station IS2.

[0108] The second thermal treatment module PM4 thermally treats the substrate W. The second thermal treatment module PM4 may include a post-exposure bake (PEB) unit that heat-treats the substrate W after exposure. The second thermal treatment module PM4 may include a temperature adjustment unit that adjusts the temperature of the substrate W. The second thermal treatment module PM4 may include a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Alternatively, the second thermal treatment module PM4 may include one or more of these units. Each of these units may have one or more thermal treatment devices. The multiple thermal treatment devices may be configured by stacking thermal treatment devices. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1). The thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0109] The measurement module PM5 measures the substrate W. In one embodiment, the measurement module PM5 includes an imaging unit including a mounting stage for mounting the substrate W, an imaging device, an illumination device, and various sensors (temperature sensor, reflectance measurement sensor, etc.). The imaging device may be, for example, a CCD camera that captures an image of the appearance of the substrate W, or a hyperspectral camera that captures images by dispersing light into wavelengths. The hyperspectral camera can measure one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film.

[0110] The developing module PM6 develops the substrate W. In one embodiment, the developing module PM6 includes a dry developing unit that dry develops the substrate W. The dry developing unit may be, for example, a thermal processing apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0111] The third thermal treatment module PM7 performs a thermal treatment on the substrate W. The third thermal treatment module PM7 may include a post-bake (PB) unit that performs a thermal treatment on the substrate W after development. The third thermal treatment module PM7 may include a temperature adjustment unit that adjusts the temperature of the substrate W. The third thermal treatment module PM7 may include a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Alternatively, the third thermal treatment module PM7 may include one or more of these units. Each of these units may have one or more thermal treatment devices. The multiple thermal treatment devices may be configured by stacking thermal treatment devices. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1). The thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0112] The second carrier station CS2 transfers the second carrier C2 to and from a system external to the substrate processing system SS. The configuration and functions of the second carrier station CS2 may be the same as those of the first carrier station CS1 described above.

[0113] The control unit CT controls each component of the substrate processing system SS to perform the above-mentioned series of processes on the substrate W. The control unit CT stores a recipe in which the process procedure, process conditions, transport conditions, etc. are set. The control unit CT controls each component of the substrate processing system SS in accordance with the recipe. The control unit CT may have some or all of the functions of the control units (control unit 200, control unit 2, control unit 400) shown in FIGS. 1 to 4.

[0114] [Example of substrate processing method] FIG. 19 is a flowchart of a substrate processing method (hereinafter referred to as "method MT4") according to one exemplary embodiment. As shown in FIG. 19, method MT4 includes steps ST100 to ST900. Step ST100 is a step of performing pre-processing on a substrate. Step ST200 is a step of forming a resist film on a substrate W. Step ST300 is a step of performing a heat treatment (pre-bake: PAB) on the substrate W on which the resist film has been formed. Step ST400 is a step of exposing the substrate W to EUV light. Step ST500 is a step of performing a heat treatment (post-exposure bake: PEB) on the exposed substrate W. Step ST600 is a step of measuring the substrate W. Step ST700 is a step of developing the resist film on the substrate W. Step ST800 is a step of performing a heat treatment (post-bake: PB) on the developed substrate W. Step ST900 is a step of etching the substrate W. Method MT4 may not include one or more of the above steps. For example, method MT4 may not include step ST600, or step ST700 may be performed after step ST500.

[0115] The method MT4 may be performed using the substrate processing system SS shown in Fig. 18. In the following explanation, an example will be given in which the control unit CT of the substrate processing system SS controls each part of the substrate processing system SS to perform the method MT4 on the substrate W.

[0116] (Process ST100: Pretreatment) First, a first carrier C1 containing a plurality of substrates W is loaded into a first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on a first mounting plate ST1. Next, the first transfer device HD1 sequentially removes each substrate W from the first carrier C1 and transfers them to a second transfer device HD2 in the first processing station PS1. The substrates W are transferred to a pre-processing module PM1 by the second transfer device HD2. The substrates W are pre-processed by the pre-processing module PM1. The pre-processing may include, for example, one or more of temperature adjustment of the substrate W, forming a part or all of an undercoat film on the substrate W, heating the substrate W, and high-precision temperature adjustment of the substrate W. The pre-processing may also include a surface modification process of the substrate W.

[0117] (Step S200: Resist film formation) Next, the substrate W is transported to the resist film formation module PM2 by the second transport device HD2. A resist film is formed on the substrate W by the resist film formation module PM2. In one embodiment, the resist film is formed by a wet process such as a solution coating method. For example, the resist film is formed by spin-coating the resist film on the substrate W using a wet coating unit of the resist film formation module PM2. In one embodiment, the resist film is formed on the substrate W by a dry process such as a vapor deposition method. For example, the resist film is formed by vapor-depositing the resist film on the substrate W using a dry coating unit of the resist film formation module PM2.

[0118] The formation of a resist film on the substrate W may be performed using both a dry process and a wet process. For example, after a first resist film is formed on the substrate W by a dry process, a second resist film may be formed on the first resist film by a wet process. In this case, the film thickness, material, and composition of the first resist film may be the same as or different from the film thickness, material, and composition of the second resist film.

[0119] (Process ST300:PAB) Next, the substrate W is transferred to the first thermal treatment module PM3 by the second transfer device HD2. The substrate W is subjected to a heat treatment (pre-baking: PAB) by the first thermal treatment module PM3. The pre-baking may be performed in an air atmosphere or an inert atmosphere. In the pre-baking, the substrate W may be heated to 50°C or higher and 250°C or lower, 50°C or higher and 200°C or lower, or 80°C or higher and 150°C or lower. When a resist film is formed by a dry process in step ST200, the pre-baking may be performed consecutively by the dry coating unit that performed step ST200. In one embodiment, after the pre-baking, a process (Edge Bead Removal: EBR) for removing the resist film from the edge of the substrate W may be performed.

[0120] (Step ST400: EUV exposure) Next, the substrate W is transferred by the second transfer device HD2 to the third transfer device HD3 in the first interface station IS1. The substrate W is then transferred by the third transfer device HD3 to the exposure apparatus EX. The substrate W is EUV exposed through an exposure mask (reticle) in the exposure apparatus EX. As a result, a first region that is EUV exposed and a second region that is not EUV exposed are formed on the substrate W, corresponding to the pattern of the exposure mask (reticle).

[0121] (Process ST500:PEB) Next, the substrate W is transferred from the fourth transfer device HD4 in the second interface station IS2 to the fifth transfer device HD5 in the second processing station PS2. The substrate W is then transferred by the fifth transfer device HD5 to the second thermal processing module PM4, where it is subjected to a heat treatment (post-exposure bake: PEB). The post-exposure bake may be performed in an air atmosphere. In the post-exposure bake, the substrate W may be heated to a temperature of 180°C or higher and 250°C or lower.

[0122] (Process ST600: Measurement) Next, the substrate W is transported to the measurement module PM5 by the fifth transport device HD5. The measurement module PM5 measures the substrate W. The measurement may be optical measurement. In one embodiment, the measurement by the measurement module PM5 includes measuring the appearance and dimensions of the substrate W using a CCD camera. In one embodiment, the measurement by the measurement module PM5 includes measuring one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0123] In one embodiment, the control unit CT determines whether or not there is an exposure abnormality in the substrate W based on the measured appearance, dimensions, pattern shape, etc. of the substrate W. In one embodiment, if the control unit CT determines that there is an exposure abnormality in the substrate W, the substrate W may be reworked or discarded without being developed in step ST700. Reworking of the substrate W may be performed by removing the resist on the substrate W and returning to step ST200 to form a resist film again. By performing rework before development, damage to the substrate W can be avoided or suppressed.

[0124] (Process ST700: Development) Next, the substrate W is transported to the developing module PM6 by the fifth transport device HD5. In the developing module PM6, the resist film on the substrate W is developed. The developing process may be performed by dry development. The developing process in step ST700 may be performed by method MT1 or method MT2. After or during the developing process, a desorption process may be performed one or more times. The desorption process includes a process of descumming the surface of the resist film or smoothing the surface using an inert gas such as helium or a plasma of the inert gas. Furthermore, after the developing process, the developing module PM6 may etch a portion of the undercoat film UF using the developed metal-containing resist MF as a mask.

[0125] (Process ST800:PB) Next, the substrate W is transferred by the fifth transfer device HD5 to the third thermal treatment module PM7, where it is subjected to a heat treatment (post-baking). The post-baking may be performed in an air atmosphere or in a reduced-pressure atmosphere containing N2 or O2. In the post-baking, the substrate W may be heated to 150°C or higher and 250°C or lower. The post-baking may be performed by the second thermal treatment module PM4 instead of the third thermal treatment module PM7. In one embodiment, after the post-baking, the measurement module PM5 may perform optical measurement of the substrate W. This measurement may be performed in addition to or instead of the measurement in step ST600. In one embodiment, the control unit CT determines whether or not there are any abnormalities, such as defects, scratches, or foreign matter, in the developed pattern on the substrate W, based on the measured appearance, dimensions, pattern shape, and the like of the substrate W. In one embodiment, if the control unit CT determines that there is an abnormality in the substrate W, the substrate W may be reworked or discarded without being etched in step ST900. In one embodiment, when the control unit CT determines that the substrate W has an abnormality, the opening dimensions of the resist film on the substrate W may be adjusted by a dry coating unit (CVD apparatus, ALD apparatus, etc.).

[0126] (Process ST900: Etching) After step ST800 is performed, the substrate W is transferred by the fifth transfer device HD5 to the sixth transfer device HD6 in the second carrier station CS2, and then transferred by the sixth transfer device HD6 to the second carrier C2 of the second mounting plate ST2. The second carrier C2 is then transferred to a plasma processing system (not shown). In the plasma processing system, the undercoat film UF of the substrate W is etched using the developed resist film as a mask. This completes the method MT3. When the resist film is developed using a plasma processing device in step ST700, etching may be performed subsequently in the plasma processing chamber of the same plasma processing device as development. If the second processing station PS2 includes a plasma processing module in addition to the developing module PM6, etching may be performed in the plasma processing module included in the second processing station PS2. The above-described desorption process may be performed one or more times before or during etching.

[0127] Various experiments conducted to evaluate Methods MT1 to MT3 will be described below, but the experiments described below do not limit the present disclosure.

[0128] (First experiment) In the first experiment, a substrate having the same structure as the substrate W shown in FIG. 6 was prepared on a substrate support in the chamber. The metal-containing resist MF was an EUV resist containing tin (Sn). The first film UF1 was an SOG film. The second film UF2 was an SOC film. The third film UF3 was a silicon oxide film.

[0129] Thereafter, a first process gas was supplied into the chamber without generating plasma (step ST12). The first process gas was a mixture of hydrogen fluoride gas (HF gas) and argon gas. The pressure in the chamber was 106.7 Pa (0.8 Torr). The partial pressure of the hydrogen fluoride gas was 88.9 Pa (0.67 Torr). The temperature of the substrate support was 120°C.

[0130] Thereafter, a second process gas was supplied into the chamber without generating plasma (step ST13). The second process gas was a mixture of silicon tetrachloride gas (SiCl4 gas) and argon gas. The pressure in the chamber was 26.7 Pa (0.2 Torr). The partial pressure of the silicon tetrachloride gas was 2.4 Pa (0.02 Torr). The temperature of the substrate support was 120°C.

[0131] Thereafter, steps ST12 and ST13 were repeated so that each of steps ST12 and ST13 was performed five times. The number of times each of steps ST12 and ST13 was performed was defined as the number of cycles.

[0132] (Second experiment) The second experiment was carried out in the same manner as the first experiment, except that step ST13 and the repeating step were not carried out. The processing time for step ST12 was 240 seconds.

[0133] (Third experiment) The third experiment was carried out in the same manner as the first experiment, except that step ST12 and the repeating step were not carried out. The processing time for step ST13 was 240 seconds.

[0134] (Results of the first experiment) FIG. 20 is a graph showing an example of the results of the first experiment. In FIG. 20, the horizontal axis represents the number of cycles, and the vertical axis represents the film thickness of the first region MF1 and the second region MF2. As can be seen from FIG. 20, the film thickness of the second region MF2 decreases as the number of cycles increases, reaching 0 nm at the fourth cycle. This result demonstrates that the dry development was not interrupted and the second region MF2 was completely removed. The dotted lines in FIG. 20 are linear approximations of the results for the first region MF1 and the second region MF2. The film thickness removed per cycle for each of the first region MF1 and the second region MF2 was calculated from the linear approximations. The film thickness of the first region MF1 removed per cycle was 0.8 nm / cycle. The film thickness of the second region MF2 removed per cycle was 9 nm / cycle. This result demonstrates that the second region MF2 can be removed with a high selectivity relative to the first region MF1.

[0135] (Results of the second experiment) FIG. 21 is a graph showing an example of the results of the second experiment. In FIG. 21, the horizontal axis represents the time during which the processing gas is supplied, and the vertical axis represents the film thickness in the first region MF1 and the second region MF2. As can be seen from FIG. 21, the film thickness in the second region MF2 decreases until about 30 seconds after the start of the processing gas supply, but then gradually increases. In other words, if step ST13 is not performed, the dry development stops midway, and the second region MF2 is not completely removed.

[0136] (Results of the third experiment) Fig. 22 is a graph showing an example of the results of the third experiment. As can be seen from Fig. 22, the film thickness of the second region MF2 decreases from the start of the supply of the processing gas until about 120 seconds later, but then gradually increases. In other words, if step ST12 is not performed, the dry development stops midway, and the second region MF2 is not completely removed.

[0137] (Fourth experiment) In the fourth experiment, a substrate was prepared that included a metal-containing resist MF having a first region MF1 and a second region MF2. Each of the first region MF1 and the second region MF2 had a line pattern when viewed from above. Then, a process of supplying a mixed gas of hydrogen fluoride gas and argon gas to the substrate was performed for 20 seconds. Then, a process of supplying a mixed gas of silicon tetrachloride gas and argon gas to the substrate was performed for 20 seconds. In the fourth experiment, when these two processes constitute one cycle, 1 to 6 cycles could be set. The temperature of the substrate support part was set to a value between 60°C and 120°C in 20°C increments. In the fourth experiment, dry development was performed after setting the number of cycles and the temperature of the substrate support part. Then, the width of the remaining line pattern in the first region MF1 (LCD: Line Critical Dimension) and the width variation of the line pattern in the first region MF1 (LWR: Line Width Roughness) were measured for the developed substrate.

[0138] (Results of the fourth experiment) FIG. 23 is a table showing an example of the results of the fourth experiment. In FIG. 23, the horizontal columns indicate the number of cycles, and the vertical columns indicate the temperature of the substrate support. For example, the LCD and LWR measurements shown in the upper left corner indicate values ​​measured under conditions where the number of cycles was 1 and the temperature of the substrate support was 120°C. From FIG. 23, it can be seen that when the temperature of the substrate support is low, the LCD value increases and the LWR value decreases. It can also be seen that when the temperature of the substrate support is 60°C, the decrease in the LCD value and the increase in the LWR value are suppressed even when the number of cycles is increased.

[0139] Various exemplary embodiments included in the present disclosure are now described in [E1] to [E23] below.

[0140] [E1] (a) providing a substrate on a substrate support in a chamber, the substrate comprising an liner and a metal-containing resist on the liner, the metal-containing resist having a first area that is exposed and a second area that is not exposed; (b) supplying a first process gas containing a fluorine-containing gas into the chamber to form a metal fluoride layer on the surface of the second region; (c) removing the metal fluoride layer by supplying a second process gas into the chamber, the second process gas comprising a chlorine-containing gas; A dry development method comprising:

[0141] [E2] The dry development method according to [E1], wherein the metal-containing resist contains at least one selected from the group consisting of tin, hafnium, and titanium.

[0142] [E3] The dry development method according to [E1] or [E2], wherein the metal-containing resist is an EUV resist.

[0143] [E4] The dry development method according to any one of [E1] to [E3], wherein in (b), the metal fluoride layer is formed without generating plasma.

[0144] [E5] The dry development method according to [E4], wherein the fluorine-containing gas contains at least one selected from the group consisting of hydrogen fluoride gas and xenon fluoride gas.

[0145] [E6] The dry development method according to any one of [E1] to [E5], wherein in (b), the metal fluoride layer is generated using plasma generated from the fluorine-containing gas.

[0146] [E7] The dry development method according to [E6], wherein the fluorine-containing gas includes at least one selected from the group consisting of hydrogen fluoride gas, xenon fluoride gas, nitrogen fluoride gas, fluorocarbon gas, hydrofluorocarbon gas, and sulfur fluoride gas.

[0147] [E8] The dry development method according to any one of [E1] to [E7], wherein in (b), the temperature of the substrate support part is 30° C. or higher.

[0148] [E9] The dry developing method according to any one of [E1] to [E8], wherein the chlorine-containing gas includes at least one selected from the group consisting of silicon tetrachloride gas, titanium tetrachloride gas, dimethylaluminum chloride gas, thionyl chloride gas, and acetyl chloride gas.

[0149] [E10] The dry development method according to any one of [E1] to [E9], wherein in (c), the temperature of the substrate support part is 30° C. or higher.

[0150] [E11] (d) The dry development method according to any one of [E1] to [E10], further comprising a step of repeating (b) and (c).

[0151] [E12] The above (d) is changing at least one selected from the group consisting of the pressure in the chamber, the temperature of the substrate support part, the treatment time of (b), and the treatment time of (c) according to the aspect ratio of the recess formed in the metal-containing resist in (c); The dry development method according to [E11], comprising:

[0152] [E13] The above (d) is performing at least one of reducing the pressure in the chamber, reducing the temperature of the substrate support, shortening the processing time of (b), and shortening the processing time of (c) in response to an increase in the aspect ratio of the recesses formed in the metal-containing resist in (c); The dry development method according to [E11] or [E12], comprising:

[0153] [E14] The above (d) is a first period in which (b) is executed in a first processing time and (c) is executed in a second processing time; a second period after the first period in which (b) is performed for a third processing time shorter than the first processing time, and (c) is performed for a fourth processing time shorter than the second processing time; The dry development method according to any one of [E11] to [E13], comprising:

[0154] [E15] In the above (d), one of the first process gas and the second process gas is supplied sequentially into the chamber; the other of the first process gas and the second process gas is supplied into the chamber at a first gas flow rate and a second gas flow rate that is smaller than the first gas flow rate. The dry development method according to any one of [E11] to [E14].

[0155] [E16] The above (b) is forming the metal fluoride layer without generating a plasma; generating a plasma from the first process gas to form the metal fluoride layer; The dry development method according to any one of [E1] to [E15], comprising:

[0156] [E17] The dry development method according to any one of [E1] to [E16], further comprising a step of purging the internal space of the chamber at least one of after (b) and after (c).

[0157] [E18] The dry developing method according to any one of [E1] to [E17], wherein the thickness of the second region removed in the direction from the metal-containing resist toward the undercoat film per one cycle including (b) and (c) is 5 nm or more and 20 nm or less.

[0158] [E19] The dry developing method according to any one of [E1] to [E18], wherein the partial pressure of the chlorine-containing gas is 13.3 Pa or more and 13.3 kPa or less.

[0159] [E20] (b) is carried out at a first temperature; The dry developing method according to any one of [E1] to [E19], wherein the step (c) is carried out at a second temperature higher than the first temperature.

[0160] [E21] (a) providing a substrate on a substrate support in a chamber, the substrate comprising an liner and a metal-containing resist on the liner, the metal-containing resist having a first area that is exposed and a second area that is not exposed; (b) removing the second region by supplying a process gas into the chamber, the process gas including a fluorine-containing gas and a chlorine-containing gas; A dry development method comprising:

[0161] [E22] The dry development method according to [E21], wherein (b) includes reducing the pressure in the chamber in accordance with an increase in the aspect ratio of the recess formed in the metal-containing resist.

[0162] [E23] a chamber; a substrate support for supporting a substrate in the chamber, the substrate comprising an undercoat film and a metal-containing resist on the undercoat film, the metal-containing resist having a first exposed area and a second unexposed area; a gas supply configured to supply a first process gas comprising a fluorine-containing gas and a second process gas comprising a chlorine-containing gas into the chamber; A control unit; Equipped with The control unit supplying the first process gas into the chamber to form a metal fluoride layer on the surface of the second region; a dry development apparatus configured to control the gas supply unit to supply the second process gas into the chamber to remove the metal fluoride layer. [Explanation of symbols]

[0163] 1,100...dry developing apparatus, 10,102...chamber (processing chamber), 11,121...substrate support part, 2,200...control part, 20,170...gas supply part, UF...undercoat film, MF...metal-containing resist, MF1...first region, MF2...second region, MF21...metal fluoride layer, MT1, MT2, MT3...dry developing method, W...substrate.

Claims

1. (a) providing a substrate on a substrate support in a chamber, the substrate comprising an liner and a metal-containing resist on the liner, the metal-containing resist having a first area that is exposed and a second area that is not exposed; (b) supplying a first process gas containing a fluorine-containing gas into the chamber to form a metal fluoride layer on the surface of the second region; (c) removing the metal fluoride layer by supplying a second process gas into the chamber, the second process gas comprising a chlorine-containing gas; Including, the metal-containing resist comprises tin; The dry development method, wherein the metal-containing resist is an EUV resist.

2. 2. The dry development method according to claim 1, wherein the metal-containing resist contains at least one selected from the group consisting of hafnium and titanium.

3. 3. The dry development method according to claim 1, wherein in step (b), the metal fluoride layer is formed without generating plasma.

4. 4. The dry development method according to claim 3, wherein the fluorine-containing gas includes at least one selected from the group consisting of hydrogen fluoride gas and xenon fluoride gas.

5. 3. The dry development method according to claim 1, wherein in step (b), the metal fluoride layer is formed using plasma generated from the fluorine-containing gas.

6. 6. The dry development method according to claim 5, wherein the fluorine-containing gas includes at least one selected from the group consisting of hydrogen fluoride gas, xenon fluoride gas, nitrogen fluoride gas, fluorocarbon gas, hydrofluorocarbon gas, and sulfur fluoride gas.

7. 3. The dry development method according to claim 1, wherein in step (b), the temperature of the substrate support part is 30[deg.] C. or higher.

8. 3. The dry development method according to claim 1, wherein the chlorine-containing gas includes at least one selected from the group consisting of silicon tetrachloride gas, titanium tetrachloride gas, dimethylaluminum chloride gas, thionyl chloride gas, and acetyl chloride gas.

9. 3. The dry development method according to claim 1, wherein in step (c), the temperature of the substrate support part is 30[deg.] C. or higher.

10. The dry development method according to claim 1 or 2, further comprising the step (d) of repeating the steps (b) and (c).

11. The (d) is changing at least one selected from the group consisting of a pressure in the chamber, a temperature of the substrate support part, a processing time of the process (b), and a processing time of the process (c) according to an aspect ratio of the recess formed in the metal-containing resist in the process (c); The dry development method according to claim 10, comprising:

12. The (d) is performing at least one of reducing the pressure in the chamber, reducing the temperature of the substrate support, shortening the processing time of (b), and shortening the processing time of (c) in response to an increase in the aspect ratio of the recess formed in the metal-containing resist in (c); The dry development method according to claim 10, comprising:

13. The (d) is a first period in which (b) is performed in a first processing time and (c) is performed in a second processing time; a second period after the first period in which (b) is performed for a third processing time shorter than the first processing time, and (c) is performed for a fourth processing time shorter than the second processing time; The dry development method according to claim 10, comprising:

14. In the above (d), one of the first process gas and the second process gas is supplied sequentially into the chamber; the other of the first process gas and the second process gas is supplied into the chamber at a first gas flow rate and a second gas flow rate that is smaller than the first gas flow rate. The dry development method according to claim 10.

15. The (b) is forming the metal fluoride layer without generating a plasma; generating a plasma from the first process gas to form the metal fluoride layer; The dry development method according to claim 1 or 2, comprising:

16. 3. The dry development method according to claim 1, further comprising the step of purging the inner space of the chamber at least one of after (b) and after (c).

17. 3. The dry development method according to claim 1, wherein a thickness of the second region removed in a direction from the metal-containing resist toward the undercoat film per one cycle including (b) and (c) is 5 nm or more and 20 nm or less.

18. 3. The dry development method according to claim 1, wherein the partial pressure of the chlorine-containing gas is 13.3 Pa or more and 13.3 kPa or less.

19. (b) is carried out at a first temperature; 3. The dry development method according to claim 1, wherein the step (c) is carried out at a second temperature higher than the first temperature.

20. (a) providing a substrate on a substrate support in a chamber, the substrate comprising an liner and a metal-containing resist on the liner, the metal-containing resist having a first area that is exposed and a second area that is not exposed; (b) removing the second region by supplying a process gas into the chamber, the process gas including a fluorine-containing gas and a chlorine-containing gas; Including, the metal-containing resist comprises tin; The dry development method, wherein the metal-containing resist is an EUV resist.

21. 21. The dry development method of claim 20, wherein (b) comprises decreasing the pressure in the chamber in response to an increase in the aspect ratio of the recess formed in the metal-containing resist.

22. a chamber; a substrate support for supporting a substrate in the chamber, the substrate comprising an undercoat film and a metal-containing resist on the undercoat film, the metal-containing resist having a first exposed area and a second unexposed area; a gas supply configured to supply a first process gas comprising a fluorine-containing gas and a second process gas comprising a chlorine-containing gas into the chamber; A control unit; Equipped with The control unit supplying the first process gas into the chamber to form a metal fluoride layer on the surface of the second region; configured to control the gas supply unit to supply the second process gas into the chamber to remove the metal fluoride layer; the metal-containing resist comprises tin; The dry developing apparatus, wherein the metal-containing resist is an EUV resist.

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