Substrate processing method and substrate processing system

Abstract

A substrate processing method according to the present disclosure comprises a step for providing a substrate on a substrate support in a chamber. The substrate has a metal-containing film including a first region that has been optically exposed and a second region that has not been optically exposed. The substrate processing method further comprises a step for exposing the substrate to BCl3 gas and HBr gas to remove the second region selectively with respect to the first region and to form a recess in the metal-containing film.

Description

[Technical Field]

[0001] SUMMARY Exemplary embodiments of the present disclosure relate to a substrate processing method and a substrate processing system. [Background technology]

[0002] Patent Document 1 discloses a technique for forming a thin film on a semiconductor substrate that is patterned using extreme ultraviolet light (hereinafter referred to as "EUV"). [Prior art documents] [Patent documents]

[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 for properly developing metal-containing films. [Means for solving the problem]

[0005] In one exemplary embodiment of the present disclosure, a method for processing a substrate includes (a) providing a substrate on a substrate support in a chamber, the substrate having a metal-containing film including a first exposed region and a second unexposed region, and (b) exposing the substrate to BCl3 gas and HBr gas to selectively remove the second region relative to the first region and form a recess in the metal-containing film. [Effects of the Invention]

[0006] According to one exemplary embodiment of the present disclosure, a technique for appropriately developing metal-containing films can be provided. [Brief explanation of the drawings]

[0007] [Figure 1]FIG. 1 is a diagram illustrating an example of the configuration of a heat treatment system. [Figure 2] FIG. 1 is a diagram illustrating an example of the configuration of a plasma processing system. [Figure 3] FIG. 1 is a diagram illustrating an example of the configuration of a capacitively coupled plasma processing apparatus. [Figure 4] 4 is a flowchart showing a substrate processing method according to the first embodiment. [Figure 5] 5 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11 of the substrate processing method shown in FIG. [Figure 6] 1 is a diagram showing an example of an undercoat film UF of a substrate W. FIG. [Figure 7] 1 is a diagram showing an example of an undercoat film UF of a substrate W. FIG. [Figure 8] Figure 8(a) shows the top surface (plan) and cross section of the metal-containing film MF after exposure, and Figure 8(b) shows the top surface (plan) and cross section of the metal-containing film MF developed using a conventional developing gas. [Figure 9] FIG. 9(a) is a cross-sectional view of an example substrate including a protective portion, and FIG. 9(b) is a diagram for explaining the effect of the protective portion in one embodiment. [Figure 10] FIG. 2 is a diagram showing an example of the cross-sectional structure of the substrate W after development. [Figure 11] FIG. 11(a) is a schematic cross-sectional view showing another example of the configuration of the heat treatment system, and FIG. 11(b) is a schematic plan view showing another example of the configuration of the heat treatment system. [Figure 12] 3A and 3B are schematic diagrams illustrating an example of the configuration of a substrate support portion. [Figure 13] 10 is a flowchart illustrating a method MT2. [Figure 14] FIG. 2 is a block diagram for explaining an example of the configuration of a substrate processing system SS. [Figure 15] 1 is a flowchart illustrating a method MT. [Figure 16] FIGS. 16(a) and 16(b) are timing charts of an example of a development process performed according to either method MT1 or method MT2. [Figure 17]10 is a timing chart of an example of a development process performed according to a method MT2. [Figure 18] 10 is a timing chart of an example of a development process performed according to a method MT2. [Figure 19] 10 is a graph showing the results of a first experiment. [Figure 20] 10 is a graph showing the results of a second experiment. [Figure 21] 10 is a graph showing the results of a third experiment. DETAILED DESCRIPTION OF THE INVENTION

[0008] According to one exemplary embodiment of the present disclosure, a method for processing a substrate includes: (a) providing a substrate on a substrate support in a chamber, the substrate having a metal-containing film including a first exposed region and a second unexposed region; and (b) exposing the substrate to BCl3 gas and HBr gas to selectively remove the second region relative to the first region and form a recess in the metal-containing film.

[0009] Hereinafter, each embodiment of the present disclosure will be described in detail with reference to the drawings. In each drawing, the same or similar elements are designated by the same reference numerals, and redundant explanations will be omitted. Unless otherwise specified, the positional relationships, such as up, down, left, and right, will be described based on the positional relationships shown in the drawings. The dimensional ratios in the drawings do not represent actual ratios, and the actual ratios are not limited to the ratios shown in the drawings.

[0010] <Example of heat treatment system configuration>

[0011] 1 is a diagram illustrating an example of the configuration of a heat treatment system. In one embodiment, the heat treatment system includes a heat treatment apparatus 100 and a control unit 200. The heat treatment system is an example of a substrate treatment system, and the heat treatment apparatus 100 is an example of a substrate treatment apparatus.

[0012] The heat treatment apparatus 100 has a process chamber 102 that can be sealed. The process chamber 102 is, for example, an airtight cylindrical container, and is configured so that the internal atmosphere can be adjusted. A side wall heater 104 is provided on the side wall of the process chamber 102. A ceiling heater 130 is provided on the ceiling wall (top plate) of the process chamber 102. A ceiling surface 140 of the ceiling wall (top plate) of the process chamber 102 is formed as a horizontal, flat surface, and its temperature is adjusted by the ceiling heater 130.

[0013] A substrate support 121 is provided at the lower side of the processing chamber 102. The substrate support 121 constitutes a mounting portion on which the substrate W is mounted. The substrate support 121 is formed, for example, in a circular shape in a plan view, and the substrate W is mounted on its horizontally formed surface (top surface). A stage heater 120 is embedded within the substrate support 121. This stage heater 120 can heat the substrate W mounted on the substrate support 121. A ring assembly (not shown) may be disposed in the substrate support 121 to surround the substrate W. The ring assembly may include one or more annular members. By disposing the ring assembly around the substrate W, temperature controllability in the outer peripheral region of the substrate W can be improved. The ring assembly may be made of an inorganic material or an organic material depending on the desired heat treatment.

[0014] The substrate support 121 is supported within the processing chamber 102 by support columns 122 provided on the bottom surface of the processing chamber 102. A plurality of lift pins 123 that can be raised and lowered vertically are provided on the circumferential outer sides of the support columns 122. Each of the lift pins 123 is inserted into a through-hole provided in the substrate support 121. The lift pins 123 are arranged at intervals in the circumferential direction. The lift pins 123 are raised and lowered by a lift mechanism 124. When the lift pins 123 protrude from the surface of the substrate support 121, the substrate W can be transferred between a transport mechanism (not shown) and the substrate support 121.

[0015] An exhaust port 131 having an opening is provided in the sidewall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump, a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. The pressure inside the processing chamber 102 is adjusted by adjusting the exhaust flow rate, etc., using the exhaust mechanism 132. Note that a transfer port for a substrate W (not shown) that can be opened and closed is formed in the sidewall of the processing chamber 102 at a position different from the position where the exhaust port 131 opens.

[0016] Furthermore, a gas nozzle 141 is provided on the sidewall of the processing chamber 102 at a position different from the exhaust port 131 and the transfer port for the substrate W. The gas nozzle 141 supplies processing gas into the processing chamber 102. The gas nozzle 141 is provided on the sidewall of the processing chamber 102 on the opposite side from the exhaust port 131 when viewed from the center of the substrate support 121. That is, the gas nozzle 141 is provided on the sidewall of the processing chamber 102 symmetrically to the exhaust port 131 with respect to a vertical imaginary plane that passes through the center of the substrate support 121.

[0017] The gas nozzle 141 is formed in a rod shape that protrudes from the sidewall of the processing chamber 102 toward the center of the processing chamber 102. The tip of the gas nozzle 141 extends, for example, horizontally from the sidewall of the processing chamber 102. The processing gas is discharged into the processing chamber 102 from a discharge port that opens at the tip of the gas nozzle 141, flows in the direction of the dashed-dotted arrow shown in FIG. 1 , and is exhausted from the exhaust port 131. The tip of the gas nozzle 141 may have a shape that extends obliquely downward toward the substrate W, or may have a shape that extends obliquely upward toward the ceiling surface 140 of the processing chamber 102.

[0018] 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.

[0019] The heat treatment apparatus 100 has a gas supply pipe 152 connected to a gas nozzle 141 from outside the processing chamber 102. A piping heater 160 for heating the gas in the gas supply pipe 152 is provided around the gas supply pipe 152. The gas supply pipe 152 is connected to a gas supply unit 170. The gas supply unit 170 includes at least one gas source and at least one flow rate controller. The gas supply unit may include a vaporizer that vaporizes a liquid material.

[0020] 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).

[0021] <Configuration example of plasma processing system>

[0022] FIG. 2 is a diagram illustrating an example of the configuration of a plasma processing system used as a development processing system. In one embodiment, the plasma processing system includes a plasma processing device 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing device 1 is an example of a substrate processing device. The plasma processing device 1 includes a plasma processing chamber (hereinafter simply referred to as a "processing chamber") 10, a substrate support 11, and a plasma generation unit 12. The plasma processing chamber 10 has a plasma processing space. The plasma processing chamber 10 also has at least one gas supply port for supplying at least one processing gas to the plasma processing space and at least one gas exhaust port for exhausting gas from the plasma processing space. The gas supply port is connected to a gas supply unit 20 (described later), and the gas exhaust port is connected to an exhaust system 40 (described later). The substrate support 11 is disposed in the plasma processing space and has a substrate support surface for supporting a substrate.

[0023] 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.

[0024] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various steps described in this disclosure. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to perform the various steps described herein. In one embodiment, some or all of the control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 is realized by, for example, a computer 2a. The control unit 2 may include a processing unit 2a1, a memory unit 2a2, and a communication interface 2a3. Each component of the control unit 2 may be similar to each component of the control unit 200 (see FIG. 1) described above.

[0025] The following describes a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1. Fig. 3 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0026] 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.

[0027] 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.

[0028] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive member. The conductive member of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is disposed on the base 1110. The electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within the ceramic member 1111a. The ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that the annular region 111b may also be provided by another member surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member. In this case, the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating member, or may be disposed on both the electrostatic chuck 1111 and the annular insulating member. Furthermore, at least one RF / DC electrode coupled to an RF power supply 31 and / or a DC power supply 32, which will be described later, may be disposed within the ceramic member 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or a DC signal, which will be described later, is supplied to the at least one RF / DC electrode, the RF / DC electrode is also called a bias electrode. Note that the conductive member of the base 1110 and the at least one RF / DC electrode may function as multiple lower electrodes. Alternatively, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support 11 includes at least one lower electrode.

[0029] 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.

[0030] The substrate support 11 may also include a temperature adjustment module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature adjustment module may include a heater, a heat transfer medium, a flow passage 1110a, or a combination thereof. A heat transfer fluid such as brine or a gas flows through the flow passage 1110a. In one embodiment, the flow passage 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111. The substrate support 11 may also include a heat transfer gas supply configured to supply a heat transfer gas to a gap between the backside of the substrate W and the central region 111a.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] The second RF generating unit 31b is coupled to at least one lower electrode via at least one impedance matching circuit and is configured to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF 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.

[0036] The power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generator 32a and a second DC generator 32b. In one embodiment, the first DC generator 32a is connected to at least one lower electrode and configured to generate a first DC signal. The generated first DC signal is applied to the at least one lower electrode. In one embodiment, the second DC generator 32b is connected to at least one upper electrode and configured to generate a second DC signal. The generated second DC signal is applied to the at least one upper electrode.

[0037] 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.

[0038] 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.

[0039] <Substrate processing method>

[0040] Various embodiments of the substrate processing method according to the present disclosure will be described below.

[0041] [First embodiment]

[0042] 4 is a flowchart showing a substrate processing method according to a first embodiment (hereinafter also referred to as "method MT1"). As shown in FIG. 4, method MT1 includes a step ST11 of providing a substrate and a step ST12 of supplying a processing gas. Method MT1 may include a step ST13 after step ST12 of determining whether a predetermined condition is satisfied.

[0043] The method MT1 may be performed using any one of the substrate processing systems described above (see FIGS. 1 to 3), or may be performed using two or more of these substrate processing systems. For example, the method MT1 may be performed in a heat treatment system (see FIG. 1). Below, the method MT1 will be described using an example in which the control unit 200 controls each unit of the heat treatment apparatus 100 to apply the method MT1 to the substrate W.

[0044] (Process ST11: Providing the substrate)

[0045] First, in step ST11, a substrate W is provided in the processing chamber 102 of the heat treatment apparatus 100. The substrate W is provided on the substrate support 121 via lift pins 123. After the substrate W is placed on the substrate support 121, the temperature of the substrate support 121 is adjusted to a set temperature. The temperature adjustment of the substrate support 121 may be performed by controlling the output of one or more heaters selected from the sidewall heater 104, the stage heater 120, the ceiling heater 130, and the piping heater 160 (hereinafter collectively referred to as "each heater"). In method MT1, the temperature of the substrate support 121 may be adjusted to the set temperature before step ST11. That is, the substrate W may be provided on the substrate support 121 after the temperature of the substrate support 121 is adjusted to the set temperature.

[0046] 5 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11 of the substrate processing method shown in FIG. The substrate W includes an underlayer film UF and a metal-containing film MF formed on the underlayer film UF. The substrate W may be used in the manufacture of semiconductor devices. Semiconductor devices include, for example, memory devices such as DRAMs and 3D-NAND flash memories, and logic devices.

[0047] The metal-containing film MF is a metal-containing resist film containing a metal. For example, the metal may include at least one metal selected from the group consisting of Sn (tin), Hf (hafnium), and Ti (titanium). For example, the metal-containing film MF contains Sn and may include tin oxide (Sn—O bond) and tin hydroxide (Sn—OH bond). The metal-containing film MF may further include an organic material.

[0048] 5, the metal-containing film 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 light. The second region MF2 may be an unexposed region that is not exposed to EUV light.

[0049] The undercoat film UF may be an organic film, a dielectric film, a metal film, a semiconductor film, or a laminated film of these formed on a silicon wafer.

[0050] 6 and 7 are diagrams showing examples of an undercoat film UF of a substrate W. As shown in Fig. 6, the undercoat film UF may be composed of a first film UF1, a second film UF2, and a third film UF3. As shown in Fig. 7, the undercoat film UF may be composed of a second film UF2 and a third film UF3.

[0051] The first film UF1 is, for example, a spin-on-glass (SOG) film, a SiC film, a SiON film, a Si-containing anti-reflective coating (SiARC), or an organic film. The second film UF2 is, for example, a spin-on-carbon (SOC) film, an amorphous carbon film, or a silicon-containing film. The third film UF3 is, for example, a silicon-containing film. The silicon-containing film is, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbonitride film, a polycrystalline silicon film, or a carbon-containing silicon film. The third film UF3 may be composed of multiple types of stacked silicon-containing films. For example, the third film UF3 may be composed of alternately stacked silicon oxide films and silicon nitride films. The third film UF3 may also be composed of alternately stacked silicon oxide films and polycrystalline silicon films. The third film UF3 may also be a stacked film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. The third film UF3 may also be composed of stacked silicon oxide films and silicon carbonitride films. The third film UF3 may also be a laminated film including a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.

[0052] In one embodiment, the substrate W is formed as follows. First, a metal-containing photoresist film is formed on an underlayer film that has been subjected to adhesion improvement treatment, etc. The film formation may be performed by a dry process, a wet process such as a solution coating method, or both a dry process and a wet process. Note that a surface modification process may be performed on the underlayer film before the photoresist film is formed. After the photoresist film is formed, the substrate is subjected to a heat treatment, i.e., a pre-bake (Post Apply Bake: PAB). An additional heat treatment may be performed after the pre-bake. After the heat treatment, the substrate is transferred to an exposure tool, and EUV light is irradiated onto the photoresist film through an exposure mask (reticle). This forms a substrate W having an underlayer film UF and a metal-containing film 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 (non-aperture region) on an exposure mask (reticle) that blocks EUV light. 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. After exposure, the substrate W is transferred from the exposure tool to a heat treatment device under atmosphere control and subjected to a heat treatment, i.e., post-exposure bake (PEB). After PEB, the substrate W may be subjected to an additional heat treatment.

[0053] (Step ST12: Supply of processing gas)

[0054] Step ST12 is a step of selectively removing the second region MF2 relative to the first region MF1 by exposing the substrate to a processing gas. That is, in step ST12, the metal-containing film MF is developed using the processing gas. As shown in FIG. 8(a), the first region MF1 of the metal-containing film MF may include a highly exposed region EX1 and an intermediately exposed region EX2. The highly exposed region EX1 is a region at or near the center of the first region MF1, where the exposure dose is sufficient. That is, the highly exposed region EX1 is a region irradiated with a sufficient amount of light during exposure of the substrate W. On the other hand, the intermediately exposed region EX2 is a region closer to the second region MF2 than the highly exposed region EX1, where the exposure dose is insufficient. That is, the intermediately exposed region EX2 is a region irradiated with an insufficient amount of light during exposure of the substrate W. Because a developing gas such as HBr gas has high reactivity, the selectivity, which is the difference between the development rate of the first region MF1 and the development rate of the second region MF2, is low when using a developing gas such as HBr gas. Therefore, when the metal-containing film MF is developed using a developing gas such as HBr, not only the highly exposed region EX1 but also the intermediately exposed region EX2 may be removed, which may deteriorate the shape of the first region MF1 after development. For example, as shown in Figure 8(b), the dimension (line width) of the first region MF1 may become smaller due to development, and the cross-sectional shape may become inverted tapered.

[0055] In contrast, in step ST12, when dry development is performed on the metal-containing film MF, a process gas containing a gas containing a Lewis acid and a developing gas is used. That is, in step ST12, a process gas containing a Lewis acid gas and a developing gas is used. According to step ST12 using such a process gas, as shown in FIG. 9(a), the surface of the first region MF1 (intermediately exposed region) exposed by dry development reacts with the Lewis acid, and a protective portion PF is formed on the surface of the first region MF1. The surface on which the protective portion PF is formed includes the sidewall that defines the recess formed in step ST12. FIG. 9(b) is a diagram for explaining the effect of the protective portion PF in one embodiment. FIG. 9(b) shows an example of dry development of a metal-containing film MF containing Sn using a process gas containing BCl3 gas as the Lewis acid gas and HBr gas as the developing gas. As shown in FIG. 9(b), Sn-O bonds exist on the surface of the first region MF1 exposed by dry development. When this surface comes into contact with BCl3 gas, O-B bonds are formed, preventing contact between the surface of the first region MF1 and HBr gas. That is, the protective portion containing boron or the region containing a boron-oxygen bond prevents contact between the surface of the first region MF1 and HBr gas. As a result, as shown in FIG. 10, the recess RE can be formed by development while suppressing the reaction between the first region MF1 and the developing gas, and the shape of the first region MF1 after development can be made closer to a vertical shape. That is, step ST12 can make the shape of the sidewall of the first region MF1 closer to a vertical shape. Furthermore, step ST12 can prevent a reduction in the dimension (line width) of the first region MF1 due to development. As a result, method MT1 can reduce the exposure dose required to obtain desired dimensions (e.g., line width). That is, method MT1 can improve sensitivity. Furthermore, according to method MT1, the roughness of the developed metal-containing film MF, for example, LWR (Line Width Roughness), can be reduced.

[0056] In one embodiment, the gas containing a Lewis acid may contain at least one selected from the group consisting of BX3, AlX3, FeX3, GaX3, SbX5, InX3, SO2, and SO3. Here, X is at least one selected from F, Cl, Br, I, H, R, and OR, and R is Me, Et, Pr, i-Pr, Bu, i-Bu, s-Bu, t-Bu, or the like. That is, R is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group. OR is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, or a tert-butoxy group. The developing gas may be a gas containing at least one selected from the group consisting of HBr, HCl, and a carboxylic acid. In one example of step ST12, BCl3 gas can be used as the gas containing Lewis acid, and HBr gas can be used as the developing gas. In this example of step ST12, BCl3 gas and HBr gas can be supplied simultaneously.

[0057] In one embodiment, the flow rate of the gas containing a Lewis acid in the processing gas may be lower than the flow rate of the developing gas. For example, when BCl3 gas and HBr gas are used as the processing gas, the ratio of the flow rate of the BCl3 gas to the flow rate of the HBr gas may be controlled to a range of 0.1 to 0.7. When the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of HBr is 0.1 or higher, the above-mentioned effects can be sufficiently obtained. On the other hand, when the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of the developing gas is 0.7 or lower, development defects such as roughness deterioration and / or scum can be sufficiently suppressed. Note that the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of the developing gas may be changed during the period in which step ST12 is performed. For example, the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of the developing gas may be increased or decreased depending on the aspect ratio of the recesses formed in step ST12.

[0058] In one embodiment, the temperature of the substrate support 121 may be controlled to a given temperature during step ST12. For example, when BCl3 gas and HBr gas are used as process gases, the temperature of the substrate support 121 may be controlled to 120° C. or less or 100° C. or less during the period when step ST12 is being performed. If the temperature of the substrate support 121 is 120° C. or less or 100° C. or less, a high selectivity can be obtained, the shape of the first region MF1 after development can have a high verticality, and a reduction in the dimension (line width) of the first region MF1 due to development can be suppressed.

[0059] (Process ST13: Judgment)

[0060] The method MT1 may include step ST13 in which it is determined whether the substrate W after step ST12 satisfies a predetermined condition. The predetermined condition may be the amount of removal of the second region MF2, whether the base film UF is exposed, or the processing time of step ST12. If it is determined in step ST13 that the predetermined condition is not satisfied (if the result of the determination in step ST13 in FIG. 4 is "NO"), step ST12 may be performed again. On the other hand, if it is determined in step ST13 that the predetermined condition is satisfied (if the result of the determination in step ST13 in FIG. 4 is "YES"), the method MT1 may be terminated.

[0061] [Second embodiment]

[0062] The heat treatment system may include a heat treatment apparatus 100a shown in FIGS. 11A and 11B instead of the heat treatment apparatus 100 shown in FIG. 1. FIG. 11A is a schematic cross-sectional view illustrating an example of the configuration of the heat treatment apparatus 100a, and FIG. 11B is a schematic plan view illustrating an example of the configuration of the heat treatment apparatus 100a. The heat treatment apparatus 100a includes a shower head 141a and multiple gas nozzles 141b on a sidewall. The shower head 141a is provided on the ceiling of the processing chamber 102. The shower head 141a may be disposed to face the substrate support 121. The multiple gas nozzles 141b are provided on the sidewall of the processing chamber 102. The multiple gas nozzles 141b may be arranged, for example, at equal intervals along the circumferential direction on the sidewall of the processing chamber 102. The multiple gas nozzles 141b may include a first gas nozzle 141b1 and a second gas nozzle 141b2. The first gas nozzles 141b1 and the second gas nozzles 141b2 may be arranged alternately in the circumferential direction. The types of gases supplied into the processing chamber 102 from the shower head 141a, the first gas nozzle 141b1, and the second gas nozzle 141b2 may be the same or different. The flow rates of the gases supplied into the processing chamber 102 from the shower head 141a, the first gas nozzle 141b1, and the second gas nozzle 141b2 may be the same or different. Heaters (not shown) may be disposed on the sidewalls of the substrate support 121 and the processing chamber 102, similar to those of the heat treatment apparatus 100. A gas exhaust port (not shown) may be disposed on the bottom side of the processing chamber 102.

[0063] 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 film MF can be improved.

[0064] [Third embodiment]

[0065] As the substrate support, a substrate support 121a shown in FIG. 12 may be used instead of the substrate support 121 shown in FIG. 1. The substrate support 121a shown in FIG. 12 has multiple zones, each of which is provided with a heater electrode. The multiple zones are arranged along a plane orthogonal to the central axis of the substrate support 121a or a plane parallel to the substrate W. In the example shown in FIG. 12, the substrate support 121a has zones Z1 to Z14, each of which is provided with a heater electrode. The heater electrodes in each zone are configured to be able to receive power independently. In other words, the substrate support 121a is configured to allow independent temperature control for each zone. Such a substrate support 121a can improve the in-plane uniformity in the development of the metal-containing film MF.

[0066] [Fourth embodiment]

[0067] The method MT1 may be performed using a plasma processing apparatus 1 instead of the heat treatment apparatus 100a. In this case, in step ST12, the second region may be selectively removed relative to the first region by exposing the substrate W to plasma generated from a processing gas in the plasma processing apparatus 1. The processing gas may be the same as the processing gas in the first embodiment.

[0068] [Fifth embodiment]

[0069] In the substrate processing method of the present disclosure, before starting substrate processing (development), a precoat may be applied to parts inside the processing chamber 102, such as the sidewalls and / or the substrate support 121 (hereinafter also referred to as "chamber parts"). The precoat may be applied by atomic layer deposition (hereinafter also referred to as "ALD"), chemical vapor deposition (hereinafter also referred to as "CVD"), or the like. A gas capable of forming a film resistant to a processing gas containing at least one selected from the group consisting of HBr, HCl, a carboxylic acid, and a Lewis acid gas may be selected. As described above, the Lewis acid gas may contain at least one selected from the group consisting of BX3, AlX3, FeX3, GaX3, SbX5, InX3, SO2, and SO3. For example, a silicon-containing gas such as aminosilane or SiCl4 may be used as the gas for forming the precoat film. In this case, a silicon oxide film may be formed as a pre-coat film on the sidewalls and / or parts inside the processing chamber 102. This can suppress corrosion of the sidewalls and / or the substrate support 121 of the processing chamber 102 by the processing gas.

[0070] Alternatively, or in addition to the pre-coating, the sidewalls and / or internal components of the process chamber 102 may be made of a material resistant to a process gas containing at least one selected from the group consisting of HBr, HCl, a carboxylic acid, and a Lewis acid gas, which may include at least one selected from the group consisting of BX3, AlX3, FeX3, GaX3, SbX5, InX3, SO2, and SO3, as described above.

[0071] In the substrate processing method of the present disclosure, the processing chamber 102 may be cleaned after the substrate processing (development). In this case, cleaning gas may be supplied into the processing chamber 102 and cleaning may be performed by heat. For example, the processing chamber 102 and its internal components may be heated before supplying the cleaning gas into the processing chamber 102. Alternatively, cleaning may be performed by supplying a cleaning gas into the processing chamber 102 and generating plasma from the cleaning gas. The cleaning gas may contain at least one of H, HBr, HCl, BCl, Cl, CHOH, CHOH, CH, and O, or may contain an inert gas such as Ar and / or N. Alternatively, cleaning may be performed by thermal atomic layer etching (hereinafter also referred to as "thermal ALE"). For example, cleaning may be performed by thermal atomic layer etching in which a fluorine-containing gas and a chlorine-containing gas are alternately supplied. This allows removal of metal oxides that adhere to the sidewalls of the processing chamber 102 and / or parts inside the chamber during development.

[0072] [Sixth embodiment]

[0073] In the substrate processing method according to the sixth embodiment, the base film UF is etched using the metal-containing film 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. In one embodiment, the etching of the base film UF may be performed by the plasma processing apparatus 1 shown in FIG. 3.

[0074] [Seventh embodiment]

[0075] FIG. 13 is a flowchart showing a substrate processing method according to a second embodiment (hereinafter also referred to as "method MT2"). In step ST21 of method MT2, a substrate is provided as in step ST11. The substrate may be the same as substrate W of the first embodiment. In method MT2, a first process gas containing a gas containing a Lewis acid is supplied into the process chamber 102 in the subsequent step ST22, and a second process gas containing a developing gas is supplied into the process chamber 102 in step ST23. That is, method MT2 differs from method MT1 in that it includes supplying a gas containing a Lewis acid into the process chamber 102 before the developing gas, and then supplying the developing gas thereafter. Note that the second process gas may further contain a gas containing a Lewis acid. Method MT2 may include step ST24, after step ST23, in which it is determined whether a predetermined condition is satisfied.

[0076] In one embodiment, the gas containing a Lewis acid (Lewis acid gas) in method MT2 may be the same as the gas containing a Lewis acid in method MT1, and the developing gas in method MT2 may be the same as the developing gas in method MT1.

[0077] The flow rate of the gas containing a Lewis acid in the second process gas may be lower than the flow rate of the developing gas. For example, when BCl3 gas and HBr gas are used as the second process gas, the ratio of the flow rate of BCl3 gas to the flow rate of HBr gas in the second process gas may be controlled to a range of 0.1 to 0.7. When the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of HBr gas is 0.1 or higher, the above-mentioned effects can be sufficiently obtained. On the other hand, when the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of the developing gas is 0.7 or lower, development defects such as roughness deterioration and / or scum can be sufficiently suppressed. Note that the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of the developing gas may be changed during the period in which step ST23 is performed. For example, the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of the developing gas may be increased or decreased depending on the aspect ratio of the recesses formed in step ST23.

[0078] The first processing gas may contain a developing gas in addition to the gas containing a Lewis acid, in which case the flow rate of the developing gas in the first processing gas may be lower than the flow rate of the gas containing a Lewis acid.

[0079] In one embodiment, the temperature of the substrate support 121 may be controlled to a predetermined temperature during steps ST22 and ST23. For example, when BCl3 gas is used as the first process gas and BCl3 gas and HBr gas are used as the second process gas, the temperature of the substrate support 121 may be controlled to 120°C or less or 100°C or less during steps ST22 and ST23. A temperature of the substrate support 121 of 120°C or less or 100°C or less can achieve a high selectivity, a highly vertical shape of the first region MF1 after development, and suppress a reduction in the dimension (e.g., linewidth) of the first region MF1 due to development. As a result, method MT2 can reduce the exposure dose required to obtain a desired dimension (e.g., linewidth). That is, method MT2 can improve sensitivity. Furthermore, method MT2 can reduce the roughness of the developed metal-containing film MF.

[0080] In one embodiment, the processing time of step ST22 may be shorter than the processing time of step ST23. In one example, the ratio of the processing time of step ST22 to the processing time of step ST23 may be controlled to 0.5 or less or 0.3 or less. When the ratio of the processing time of step ST22 to the processing time of step ST23 is 0.5 or less or 0.3 or less, it is possible to sufficiently suppress development defects such as deterioration of roughness and / or scum.

[0081] In one embodiment, a cycle including step ST22 and step ST23 may be repeated multiple times. In this case, step ST23 may be performed after step ST22 is performed, and the period during which step ST22 is performed and the period during which step ST23 is performed may partially overlap.

[0082] Furthermore, when a cycle including steps ST22 and ST23 is repeated multiple times, the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of the developing gas may be changed in step ST23 of each cycle or in step ST23 of a specific cycle. Furthermore, when a cycle including steps ST22 and ST23 is repeated multiple times, the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of the developing gas may be changed for each cycle.

[0083] The method MT2 may include step ST24 in which it is determined whether the substrate W after step ST23 satisfies a predetermined condition. The predetermined condition may be the amount of removal of the second region MF2, whether the base film UF is exposed, or the processing time of steps ST22 and ST23. If it is determined in step ST24 that the predetermined condition is not satisfied (if the result of the determination in step ST24 in FIG. 13 is "NO"), step ST22 may be performed again. On the other hand, if it is determined in step ST24 that the predetermined condition is satisfied (if the result of the determination in step ST24 in FIG. 13 is "YES"), the method MT2 may end.

[0084] <Configuration example of substrate processing system>

[0085] 14 is a block diagram illustrating an example configuration of a substrate processing system SS according to an exemplary embodiment. The substrate processing system SS includes a first carrier station CS1, a first processing station PS1, a first interface station IS1, an exposure apparatus EX, a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a controller CT.

[0086] The first carrier station CS1 loads and unloads the first carrier C1 between the first carrier station CS1 and a system external to the substrate processing system SS. The first carrier station CS1 has a mounting table with a plurality of first mounting plates ST1. The first carrier C1, which may contain a plurality of substrates W or be empty, is mounted on each first mounting plate ST1. The first carrier C1 has a housing capable of housing a plurality of substrates W therein. The first carrier C1 is, for example, a front-opening unified pod (FOUP).

[0087] The first carrier station CS1 also transports the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further includes a first transport device HD1. The first transport device HD1 is provided in the first carrier station CS1 so as to be located between the mounting table and the first processing station PS1. The first transport device HD1 transports and hands over the substrate W between the first carrier C1 on each first mounting plate ST1 and the second transport device HD2 of the first processing station PS1. The substrate processing system SS may further include a load lock module. The load lock module may be provided between the first carrier station CS1 and the first processing station PS1. The internal pressure of the load lock module can be switched between atmospheric pressure and vacuum. "Atmospheric pressure" may refer to the pressure inside the first transfer device HD1. "Vacuum" refers to a pressure lower than atmospheric pressure, and may be a medium vacuum of, for example, 0.1 Pa to 100 Pa. The inside of the second transport device HD2 may be atmospheric pressure or vacuum. The load lock module may be used, for example, to transfer a substrate W from the first transport device HD1, which is at atmospheric pressure, to the second transport device HD2, which is at vacuum, and to transfer a substrate W from the second transport device HD2, which is at vacuum, to the first transport device HD1, which is at atmospheric pressure.

[0088] The first processing station PS1 performs various processes on the substrate W. In one embodiment, the first processing station PS1 includes a pre-processing module PM1, a resist film forming module PM2, and a first thermal processing module PM3 (hereinafter collectively referred to as "first substrate processing modules PMa"). The first processing station PS1 also includes a second transfer device HD2 that transfers the substrate W. The second transfer device HD2 transfers and passes the substrate W between two designated first substrate processing modules PMa, and between the first processing station PS1 and the first carrier station CS1 or the first interface station IS1.

[0089] In the pre-processing module PM1, the substrate W is subjected to pre-processing. In one embodiment, the pre-processing module PM1 includes a temperature adjustment unit that adjusts the temperature of the substrate W, a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision, and the like. In one embodiment, the pre-processing module PM1 includes a surface modification processing unit that performs surface modification processing on the substrate W. Each processing unit of the pre-processing module PM1 may be configured to include a heat treatment device 100 (see FIG. 1) and a plasma treatment device 1 (see FIGS. 2 and 3).

[0090] In the resist film formation module PM2, a resist film is formed on the substrate W. In one embodiment, the resist film formation module PM2 includes a dry coating unit. The dry coating unit forms a resist film on the substrate W using a dry process such as a vapor phase deposition method. In one example, the dry coating unit includes a CVD apparatus or an ALD apparatus that performs chemical vapor deposition of a resist film on the substrate W arranged in a chamber, or a PVD apparatus that performs physical vapor deposition of a resist film. The dry coating unit may be a thermal processing apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0091] 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.

[0092] In one embodiment, an example of the resist film forming module PM2 includes both a wet coating unit and a dry coating unit. Note that the resist film forming module PM2 can form the above-described metal-containing film MF in a state before exposure as the resist film.

[0093] In the first thermal treatment module PM3, the substrate W is subjected to a thermal treatment. In one embodiment, the first thermal treatment module PM3 includes one or more of a pre-bake (PAB) unit that performs a heat treatment on the substrate W on which a resist film has been formed, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0094] The first interface station IS1 has a third transfer device HD3. The third transfer device HD3 transfers and delivers substrates W between the first processing station PS1 and the exposure apparatus EX. The third transfer device HD3 has a housing that houses the substrates W, and may be configured so that the temperature, humidity, pressure, etc. within the housing are controllable.

[0095] The exposure apparatus EX uses an exposure mask (reticle) to expose a resist film on the substrate W. The exposure apparatus EX may be, for example, an EUV exposure apparatus having a light source that generates EUV light.

[0096] The second interface station IS2 has a fourth transport device HD4. The fourth transport device HD4 transports and delivers substrates W between the exposure apparatus EX and the second processing station PS2. The fourth transport device HD4 has a housing that houses the substrates W, and may be configured so that the temperature, humidity, pressure, etc. within the housing are controllable.

[0097] The second processing station PS2 performs various processes on the substrate W. In one embodiment, the second processing station PS2 includes a second thermal processing module PM4, a measurement module PM5, a development module PM6, and a third thermal processing module PM7 (hereinafter collectively referred to as "second substrate processing modules PMb"). The second processing station PS2 also includes a fifth transfer device HD5 that transfers the substrate W. The fifth transfer device HD5 transfers and passes the substrate W between two designated second substrate processing modules PMb, and between the second processing station PS2 and the second carrier station CS2 or the second interface station IS2.

[0098] The substrate W is subjected to a thermal treatment in the second thermal treatment module PM4. In one embodiment, the second thermal treatment module PM4 includes one or more of a post-exposure bake (PEB) unit that heat-treats the exposed substrate W, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0099] In the measurement module PM5, various measurements are performed on the substrate W. In one embodiment, the measurement module PM5 includes an imaging unit including a mounting stage for mounting the substrate W, an imaging device, an illumination device, and various sensors (temperature sensor, reflectance measurement sensor, etc.). The imaging device may be, for example, a CCD camera that captures an image of the appearance of the substrate W. Alternatively, the imaging device may be a hyperspectral camera that captures images by dispersing light into wavelengths. The hyperspectral camera can measure one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film.

[0100] In the developing module PM6, the substrate W is subjected to a developing process. In one embodiment, the developing module PM6 includes a dry developing unit that performs dry development on the substrate W. The dry developing unit may be, for example, a thermal processing apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0101] The substrate W is subjected to a thermal treatment in the third thermal treatment module PM7. In one embodiment, the third thermal treatment module PM7 includes one or more of a post-bake (PB) unit that heat-treats the substrate W after development, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0102] The second carrier station CS2 transfers the second carrier C2 between the second carrier station CS2 and a system external to the substrate processing system SS. The configuration and functions of the second carrier station CS2 may be similar to those of the first carrier station CS1 described above.

[0103] The control unit CT controls each component of the substrate processing system SS to perform a given process on the substrate W. The control unit CT stores a recipe in which the process procedure, process conditions, transport conditions, etc. are set, and controls each component of the substrate processing system SS to perform the given process on the substrate W in accordance with the recipe. The control unit CT may have some or all of the functions of the control units (control unit 200 and control unit 2) shown in FIGS. 1 to 3.

[0104] <Example of substrate processing method>

[0105] FIG. 15 is a flowchart showing a substrate processing method (hereinafter also referred to as “method MT”) according to an exemplary embodiment. As shown in FIG. 15 , method MT includes step ST100 of pre-treating a substrate, step ST200 of forming a resist film on the substrate, step ST300 of performing a heat treatment (pre-bake: PAB) on the substrate on which the resist film has been formed, step ST400 of exposing the substrate to EUV light, step ST500 of performing a heat treatment (post-exposure bake: PEB) on the exposed substrate, step ST600 of measuring the substrate, step ST700 of developing the resist film on the substrate, step ST800 of performing a heat treatment (post-bake: PB) on the developed substrate, and step ST900 of etching the substrate. Method MT may not include one or more of the above steps. For example, method MT may not include step ST600, and step ST700 may be performed after step ST500.

[0106] The method MT may be performed using a substrate processing system SS shown in Fig. 14. The following describes an example in which a control unit CT of the substrate processing system SS controls each part of the substrate processing system SS to perform the method MT on a substrate W.

[0107] (Process ST100: Pretreatment)

[0108] First, a first carrier C1 containing a plurality of substrates W is loaded into a first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on a first mounting plate ST1. Next, the first transport device HD1 sequentially removes each substrate W from the first carrier C1 and transfers them to a second transport device HD2 of the first processing station PS1. The substrates W are then transported by the second transport device HD2 to a pre-processing module PM1. The pre-processing module PM1 performs pre-processing on the substrates W. The pre-processing may include, for example, one or more of temperature adjustment of the substrates W, forming a part or all of an undercoat film on the substrates W, heating the substrates W, and high-precision temperature adjustment of the substrates W. The pre-processing may also include a surface modification process for the substrates W.

[0109] (Step S200: Resist film formation)

[0110] Next, the substrate W is transported to the resist film formation module PM2 by the second transport device HD2. A resist film is formed on the substrate W by the resist film formation module PM2. In one embodiment, the resist film is formed by a wet process such as a liquid phase deposition method. For example, a resist film is formed by spin-coating a resist film on the substrate W using a wet coating unit of the resist film formation module PM2. In one embodiment, the resist film is formed on the substrate W by a dry process such as a vapor phase deposition method. For example, a resist film is formed by vapor-depositing a resist film on the substrate W using a dry coating unit of the resist film formation module PM2.

[0111] The resist film may be formed on the substrate W using both a dry process and a wet process. For example, after a first resist film is formed on the substrate W by a dry process, a second resist film may be formed on the first resist film by a wet process. In this case, the film thickness, material, and / or composition of the first resist film and the second resist film may be the same or different.

[0112] (Process ST300:PAB)

[0113] Next, the substrate W is transported by the second transport device HD2 to the first thermal treatment module PM3. The first thermal treatment module PM3 subjects the substrate W to a heat treatment (pre-baking: PAB). The pre-baking may be performed in an air atmosphere or an inert atmosphere. The pre-baking may be performed by heating the substrate W to a temperature of 50°C to 250°C, 50°C to 200°C, or 80°C to 150°C. When a resist film is formed by a dry process in step ST200, in one embodiment, the pre-baking may be performed in the dry coating unit that performed step ST200. In one embodiment, after the pre-baking, a process (Edge Bead Removal: EBR) may be performed to remove the resist film from the edge of the substrate W.

[0114] (Step ST400: EUV exposure)

[0115] Next, the substrate W is transferred by the second transfer device HD2 to the third transfer device HD3 of the first interface station IS1. The substrate W is then transferred by the third transfer device HD3 to the exposure apparatus EX. The substrate W is subjected to EUV exposure via an exposure mask (reticle) in the exposure apparatus EX. As a result, a first region that has been EUV exposed and a second region that has not been EUV exposed are formed on the substrate W, corresponding to the pattern of the exposure mask (reticle).

[0116] (Process ST500:PEB)

[0117] Next, the substrate W is transferred from the fourth transfer device HD4 of the second interface station IS2 to the fifth transfer device HD5 of the second processing station PS2. The substrate W is then transferred by the fifth transfer device HD5 to the second thermal treatment module PM4. The substrate W is then subjected to a heat treatment (post-exposure bake: PEB) in the second thermal treatment module PM4. The post-exposure bake may be performed in an air atmosphere. The post-exposure bake may also be performed by heating the substrate W to a temperature of 120°C or higher and 250°C or lower.

[0118] (Process ST600: Measurement)

[0119] Next, the substrate W is transported to the measurement module PM5 by the fifth transport device HD5. The measurement module PM5 measures the substrate W. The measurement may be optical measurement or other measurement. In one embodiment, the measurement by the measurement module PM5 includes measurement of the appearance and / or dimensions of the substrate W using a CCD camera. In one embodiment, the measurement by the measurement module PM5 includes measurement of one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0120] In one embodiment, the control unit CT determines whether or not there is an exposure abnormality in the substrate W based on the measured appearance, dimensions, and / or pattern shape of the substrate W. In one embodiment, if the control unit CT determines that there is an exposure abnormality, the substrate W may be reworked or discarded without being developed in step ST700. Reworking of the substrate W may be performed by removing the resist on the substrate W and returning to step ST200 to form a resist film again. Reworking after development may cause damage to the substrate W, but by performing rework before development, damage to the substrate W can be avoided or suppressed.

[0121] (Process ST700: Development)

[0122] 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 descumming or smoothing the surface from the surface of the resist film and the surface of the underlayer film UF using an inert gas such as helium or a plasma of the inert gas. Furthermore, in the developing module PM6, after the developing process, a portion of the underlayer film UF may be etched using the developed metal-containing film MF as a mask.

[0123] (Process ST800:PB)

[0124] Next, the substrate W is transferred by the fifth transfer device HD5 to the third thermal treatment module PM7, where it is subjected to a heat treatment (post-bake). The post-bake may be performed in an air atmosphere or a reduced-pressure atmosphere containing N2 or O2. The post-bake may be performed by heating the substrate W to 150°C or higher and 250°C or lower. The post-bake may be performed in the second thermal treatment module PM4 instead of the third thermal treatment module PM7. In one embodiment, after the post-bake, the measurement module PM5 may perform optical measurement of the substrate W. This measurement may be performed in addition to or instead of the measurement in step ST600. In one embodiment, the controller CT determines whether or not there are any abnormalities, such as defects, scratches, or foreign matter, in the developed pattern of the substrate W, based on the measured appearance, dimensions, and / or pattern shape of the substrate W. In one embodiment, if the controller CT determines that there is an abnormality, the substrate W may be reworked or discarded without being etched in step ST900. In one embodiment, if it is determined that there is an abnormality in the control unit CT, the opening dimensions of the resist film on the substrate W may be adjusted using a dry coating unit (CVD apparatus, ALD apparatus, etc.).

[0125] (Process ST900: Etching)

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

[0127] Timing charts related to methods MT1 and MT2 will be described below with reference to Figures 16(a), 16(b), 17, and 18. Figures 16(a) and 16(b) are timing charts of an example of a development process performed according to either method MT1 or method MT2. Figures 17 and 18 are timing charts of an example of a development process performed according to method MT2.

[0128] As shown in FIG. 16(a), in step ST12 of method MT1, a Lewis acid gas and a developing gas (e.g., HBr gas) may be simultaneously supplied into the chamber (i.e., toward the substrate). As shown in FIG. 16(b), in step ST22 of method MT2, a first process gas containing a Lewis acid gas may be supplied into the chamber. In the subsequent step ST23, a second process gas containing a Lewis acid gas and a developing gas may be supplied into the chamber, i.e., toward the substrate W. Note that in the examples shown in FIGS. 16(a) and 16(b), the supply of the Lewis acid gas and the supply of the developing gas are stopped simultaneously, but the supply of the developing gas may be stopped after the supply of the Lewis acid gas is stopped.

[0129] 17 and 18, steps ST22 and ST23 of method MT2 may be performed alternately. As shown in these figures, step ST22 is performed before step ST23. The periods of steps ST22 and ST23 may not overlap or may partially overlap.

[0130] In the examples shown in each of FIGS. 17 and 18 , the flow rate of the Lewis acid gas supplied into the chamber in step ST22 is set to a flow rate L2. Meanwhile, the flow rate of the developing gas in step ST22 is set to D1. Meanwhile, the flow rate of the developing gas supplied into the chamber in step ST23 is set to a flow rate D2. Meanwhile, the flow rate of the Lewis acid gas in step ST23 is set to L1. The flow rate L1 is smaller than the flow rate L2. The flow rate L1 may be zero or greater than zero. Furthermore, the flow rate D1 is smaller than the flow rate D2. The flow rate D1 may be zero or greater than zero. The length of time for step ST22 and / or the length of time for step ST23 may be changed depending on the elapsed time of the development process. For example, the length of time for step ST22 may be increased as the development process progresses. Furthermore, the flow rates L2 and / or D2 may be changed depending on the elapsed time of the development process. For example, the flow rate D2 may be reduced to a value smaller than the flow rate L2 as the development process progresses.

[0131] 17, the temperature of the substrate support may be adjusted to temperature T1 during the alternating repetition of step ST22 and step ST23. Alternatively, as shown in FIG. 18, the temperature of the substrate support may be set to temperature T1 during the period when step ST22 and the subsequent step ST23 are performed, and step ST25 may be performed between step ST23 and the subsequent step ST22 to adjust the temperature of the substrate support to temperature T2, which is higher than temperature T1. That is, a cycle including step ST22, step ST23, and step ST25 may be repeated. In this case, it is possible to perform development while removing residue (scum) on the substrate W in step ST25. Note that the period of step ST25 does not need to overlap with the periods of step ST22 and step ST23, or they may overlap partially.

[0132] Although various exemplary embodiments have been described above, the present invention is not limited to the above-described exemplary embodiments, and various additions, omissions, substitutions, and modifications may be made. Furthermore, elements in different embodiments may be combined to form other embodiments.

[0133] The following describes experiments performed to evaluate substrate processing methods according to various exemplary embodiments.

[0134] (First experiment)

[0135] In the first experiment, the entire area of ​​the metal-containing film was exposed to light, and then the metal-containing film was exposed to a processing gas. The metal-containing film was a resist film containing tin oxide. Two processing gases were used separately. One of the two processing gases contained only HBr gas, and the other contained HBr gas and BCl3 gas. The film thickness of the metal-containing film after processing using the processing gas, i.e., the remaining film amount, was measured.

[0136] FIG. 19 shows the results of the first experiment. In the graph of FIG. 19, the horizontal axis represents the exposure dose, and the vertical axis represents the remaining film amount of the metal-containing film after processing using the processing gas. In the graph of FIG. 19, "HBr Only" represents the results when a processing gas containing only HBr gas was used, and "HBr & BCl3" represents the results when a processing gas containing HBr gas and BCl3 gas was used. As shown in FIG. 19, the remaining film amount when a processing gas containing HBr gas and BCl3 gas was used was greater than the remaining film amount when a processing gas containing only HBr gas was used. This result confirmed that sensitivity was improved by using a processing gas containing HBr gas and BCl3 gas, i.e., a processing gas containing a developing gas and a Lewis acid gas.

[0137] (Second experiment)

[0138] In the second experiment, the entire area of ​​the metal-containing film was exposed to light, and then the metal-containing film was exposed to a processing gas. The metal-containing film was a resist film containing tin oxide. Two processing gases were used separately. One of the two processing gases contained only HBr gas, and the other contained HBr gas and BCl3 gas. The flow rate ratio of the processing gas containing HBr gas and BCl3 gas (flow rate of HBr gas:flow rate of BCl3 gas) was 10:1. The film thickness of the metal-containing film after processing using the processing gas, i.e., the remaining film amount, was measured.

[0139] The results of the second experiment are shown in Figure 20. In the graph of Figure 20, the horizontal axis represents the exposure dose, and the vertical axis represents the remaining film amount of the metal-containing film after processing using the processing gas. In the graph of Figure 20, "HBr Only" represents the results when a processing gas containing only HBr gas was used. "HBr:BCl3 = 10:1 (BCl3 first added)" represents the results when only BCl3 gas was supplied first, followed by a processing gas containing HBr gas and BCl3 gas. "HBr:BCl3 = 10:1 (BCl3 simultaneous addition)" represents the results when the supplies of HBr gas and BCl3 gas were started simultaneously. "HBr:BCl3 = 10:1 (BCl3 later added)" represents the results when only HBr gas was supplied, followed by a processing gas containing HBr gas and BCl3 gas. 20, when BCl3 gas was supplied before HBr gas and when the supplies of HBr gas and BCl3 gas were started simultaneously, the residual film amount was greater than the residual film amount in other cases. From these results, it was confirmed that the sensitivity was improved by supplying BCl3 gas before HBr gas or by starting the supplies of HBr gas and BCl3 gas simultaneously, i.e., by supplying the Lewis acid gas before the developing gas or by starting the supplies of the developing gas and Lewis acid gas simultaneously.

[0140] (Third experiment)

[0141] In the third experiment, the entire area of ​​the metal-containing film was exposed to light, and then the metal-containing film was exposed to a process gas. The metal-containing film was a resist film containing tin oxide. Four separate process gases were used. The first of the four process gases contained HBr gas and BCl3 gas, with a flow rate ratio (HBr gas flow rate:BCl3 gas flow rate) of 10:7. The second of the four process gases contained HBr gas and BCl3 gas, with a flow rate ratio (HBr gas flow rate:BCl3 gas flow rate) of 10:4. The third of the four process gases contained HBr gas and BCl3 gas, with a flow rate ratio (HBr gas flow rate:BCl3 gas flow rate) of 10:1. The fourth of the four process gases contained only HBr gas. Then, the film thickness of the metal-containing film after the treatment using the treatment gas, that is, the remaining film amount, was measured.

[0142] The results of the third experiment are shown in FIG. 21. In the graph of FIG. 21, the horizontal axis represents the exposure dose, and the vertical axis represents the remaining film amount of the metal-containing film after processing using the processing gas. In the graph of FIG. 21, "HBr:BCl3 = 10:7," "HBr:BCl3 = 10:4," "HBr:BCl3 = 10:1," and "HBr:BCl3 = 10:0 (HBr Only)" represent the results when the first to fourth gases were used, respectively. As shown in FIG. 21, in all cases where the flow rate ratio was 10:7, 10:4, and 10:1, the remaining film amount was greater than the remaining film amount when a processing gas containing only HBr gas was used. This result confirmed that high sensitivity was obtained when the ratio of the flow rate of BCl3 gas to the flow rate of HBr gas was in the range of 0.1 to 0.7.

[0143] (Fourth experiment)

[0144] In the fourth experiment, a line-and-space pattern was formed by exposing a metal-containing film to EUV light and then exposing it to a process gas. The metal-containing film was a resist film containing tin oxide. Two process gases were used. One process gas contained only HBr gas, and the other contained HBr and BCl3 gas. The difference ΔCD between the maximum and minimum widths of the cross-section of the line portion in the line-and-space pattern was calculated. The difference ΔCD when using a process gas containing HBr and BCl3 gas was normalized by the difference ΔCD when using a process gas containing only HBr gas to calculate ΔCDn. The resulting value ΔCDn was 0.78. These results confirmed that using a process gas containing HBr and BCl3 gas, i.e., a process gas containing a Lewis acid gas and a developing gas, can produce a first region MF1 with high verticality.

[0145] (5th experiment)

[0146] In the fifth experiment, a line and space pattern was formed by exposing a metal-containing film to EUV light and then exposing the metal-containing film to a processing gas. The metal-containing film was a resist film containing tin oxide. Four types of processing gases were used individually. The first of the four processing gases was a gas containing HBr gas and O2 gas. The second of the four processing gases was a gas containing HBr gas and SO2 gas. The third of the four processing gases was a gas containing HBr gas and BCl3 gas. The fourth of the four processing gases was a gas containing only HBr gas. Then, when each of the four processing gases was used, the exposure dose (mJ / cm) required to form a line and space pattern including line portions with a line width of 16 nm was calculated. 2) was identified. The exposure dose required when each of the first to third gases was normalized by the exposure dose required when the fourth gas was used, i.e., the normalized exposure dose was calculated. As a result, the normalized exposure doses when the first to third gases were used were 0.92, 0.87, and 0.90. From these results, it was confirmed that sensitivity was improved by using any of the first to third gases, i.e., a process gas containing a Lewis acid gas and a developing gas. Furthermore, the LWR of the line portion obtained when each of the third gas and the fourth gas was calculated. Then, the LWR when the third gas was used was normalized by the LWR when the fourth gas was used, i.e., the normalized LWR was calculated. The obtained normalized LWR was 0.98. From these results, it was confirmed that roughness was improved by using a process gas containing HBr gas and BCl3 gas.

[0147] Various exemplary embodiments included in the present disclosure are described below in [E1] to [E19].

[0148] [E1] (a) providing a substrate on a substrate support in a chamber, the substrate having a metal-containing film including a first exposed region and a second unexposed region; (b) exposing the substrate to BCl3 gas and HBr gas to selectively remove the second region relative to the first region and form a recess in the metal-containing film; A substrate processing method comprising:

[0149] [E2] The substrate processing method according to E1, wherein in (b), the temperature of the substrate support is set to a temperature of 100° C. or less.

[0150] [E3] The substrate processing method according to E1 or E2, wherein in (b), a protective portion containing boron is formed on a sidewall that defines the recess.

[0151] [E4] The substrate processing method according to any one of E1 to E3, wherein in (b), a bond of boron and oxygen is formed on a sidewall that defines the recess.

[0152] [E5] The substrate processing method according to any one of E1 to E4, wherein (b) includes simultaneously supplying the BCl3 gas and the HBr gas into the chamber.

[0153] [E6] The above (b) is (b-1) supplying the BCl gas into the chamber prior to supplying the HBr gas; and (b-2) supplying the HBr gas after (b-1); The substrate processing method according to any one of E1 to E4, comprising:

[0154] [E7] The substrate processing method according to E6, wherein the length of time during which (b-1) is performed is shorter than the length of time during which (b-2) is performed.

[0155] [E8] The substrate processing method according to any one of E1 to E7, wherein the flow rate of the HBr gas is greater than the flow rate of the BCl3 gas.

[0156] [E9] The substrate processing method according to any one of E1 to E7, wherein a ratio of the flow rate of the BCl3 gas to the flow rate of the HBr gas is 0.1 or more.

[0157] [E10] The substrate processing method according to E9, wherein the value of the ratio is 0.7 or less.

[0158] [E11] The substrate processing method according to any one of E1 to E10, wherein the metal-containing film contains at least one selected from the group consisting of tin, hafnium, and titanium.

[0159] [E12] (a) providing a substrate on a substrate support in a chamber, the substrate having a metal-containing film including a first exposed region and a second unexposed region; (b) selectively removing the second region relative to the first region to form a recess in the metal-containing film; Including, The above (b) is (b-1) exposing the substrate to a first process gas including a Lewis acid gas for a first period of time; and (b-2) exposing the substrate to a second process gas containing a developing gas during a second period; Including, The second period of time begins at or after the start of the first period of time. Substrate processing method.

[0160] [E13] the second process gas further comprises the Lewis acid gas; The substrate processing method according to E12, wherein in the second period, the flow rate of the developing gas is greater than the flow rate of the Lewis acid gas.

[0161] [E14] The substrate processing method according to E12 or E13, wherein the ratio of the flow rate of the Lewis acid gas to the flow rate of the developing gas is 0.1 or more.

[0162] [E15] The substrate processing method according to E14, wherein the value of the ratio is 0.7 or less.

[0163] [E16] The substrate processing method according to any one of E12 to E15, further comprising alternately repeating (b-1) and (b-2).

[0164] [E17] The substrate processing method according to any one of E12 to E16, wherein the Lewis acid gas includes at least one selected from the group consisting of BX3, AlX3, FeX3, GaX3, SbX5, InX3, SO2, and SO3, wherein X is F, Br, I, H, R, or OR, wherein R is a methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group, or tert-butyl group, and OR is a methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, or tert-butoxy group.

[0165] [E18] The substrate processing method according to any one of E12 to E17, wherein the developing gas contains at least one selected from the group consisting of HBr, HCl, and a carboxylic acid.

[0166] [E19] a chamber; a substrate support disposed within the chamber; a gas supply configured to supply a gas into the chamber; a controller configured to control the gas supply unit; Equipped with the control unit is configured to expose a substrate, having a metal-containing film including an exposed first region and an unexposed second region, to BCl gas and HBr gas from the gas supply unit while the substrate is placed on the substrate support unit, to selectively remove the second region relative to the first region and form a recess in the metal-containing film. Substrate processing system.

[0167] From the foregoing, it will be understood that various embodiments of the present disclosure have been described herein for purposes of illustration, and that various modifications may be made without departing from the scope and spirit of the present disclosure. Accordingly, the various embodiments disclosed herein are not intended to be limiting, with the true scope and spirit being indicated by the appended claims. [Explanation of symbols]

[0168] 1...plasma processing apparatus, 2...control unit, 10...plasma processing chamber, 11...substrate support unit, 20...gas supply unit, 30...power supply, 100...heat processing apparatus, 102...processing chamber, 120...stage heater, 121...substrate support unit, 141...gas nozzle, 200...control unit, MF...metal-containing film, MF1...first region, MF2...second region, UF...undercoat film, W...substrate, PF...protective unit.

Claims

1. (a) providing a substrate on a substrate support in a chamber, the substrate having a metal-containing film including a first exposed region and a second unexposed region; (b) The substrate is treated with BCl ３ and exposing the metal-containing film to a nitrogen gas and a hydrogen fluoride gas to selectively remove the second region relative to the first region and form a recess in the metal-containing film. Including, the first region includes a high exposure region and a medium exposure region; the intermediate exposure region is located between the high exposure region and the second region and is exposed with an exposure amount less than that of the high exposure region; The step (b) includes forming a protective portion on the surface of the intermediate exposure region exposed by forming the recess, the protective portion preventing the intermediate exposure region from coming into contact with the HBr gas. Substrate processing method.

2. 2. The substrate processing method according to claim 1, wherein in (b), the temperature of the substrate support is set to a temperature of 100[deg.] C. or less.

3. 2. The substrate processing method according to claim 1, wherein in (b), a bond between boron and oxygen is formed on a sidewall that defines the recess.

4. The protective portion is ３ 2. The substrate processing method according to claim 1, wherein the metal-containing film is formed by bonding boron contained in the gas with oxygen in the metal-containing film.

5. (b) adding the BCl ３ 5. The substrate processing method according to claim 1, further comprising simultaneously supplying the HBr gas and the HBr gas.

6. A method of manufacturing a semiconductor device, comprising: (a) providing a substrate on a substrate support within a chamber, the substrate having a metal-containing film including a first exposed region and a second unexposed region; (b) exposing the substrate to BCl 3 gas and HBr gas to selectively remove the second region relative to the first region and form a recess in the metal-containing film; Including, The (b) is (b-1) supplying the BCl 3 gas into the chamber prior to supplying the HBr gas; and (b-2) supplying the HBr gas after (b-1); Including, The length of time during which the (b-1) is performed is shorter than the length of time during which the (b-2) is performed. Substrate processing method.

7. The flow rate of the HBr gas is ３ 5. The substrate processing method according to claim 1, wherein the flow rate of the gas is greater than the flow rate of the gas.

8. The ratio of the BCl to the flow rate of the HBr gas ３ 5. The substrate processing method according to claim 1, wherein the ratio of the gas flow rates is 0.1 or more.

9. The substrate processing method of claim 8 , wherein the value of the ratio is 0.7 or less.

10. 5. The substrate processing method according to claim 1, wherein the metal-containing film contains at least one selected from the group consisting of tin, hafnium, and titanium.

11. (a) providing a substrate on a substrate support in a chamber, the substrate having a metal-containing film including a first exposed region and a second unexposed region; (b) selectively removing the second region relative to the first region to form a recess in the metal-containing film; Including, The (b) is (b-1) exposing the substrate to a first process gas containing a Lewis acid gas for a first period of time; and (b-2) exposing the substrate to a second process gas containing a developing gas during a second period of time; Including, the first region includes a high exposure region and a medium exposure region; the intermediate exposure region is located between the high exposure region and the second region and is exposed with an exposure amount less than that of the high exposure region; the step (b) includes forming a protective portion on the surface of the intermediate exposure region exposed by forming the recess, the protective portion preventing the intermediate exposure region from coming into contact with the developing gas; Substrate processing method.

12. The substrate processing method of claim 11, wherein the second period begins at or after the start of the first period.

13. the second process gas further comprises the Lewis acid gas; 12. The substrate processing method according to claim 11, wherein the flow rate of the developing gas is greater than the flow rate of the Lewis acid gas during the second period.

14. 12. The substrate processing method according to claim 11, wherein a ratio of a flow rate of the Lewis acid gas to a flow rate of the developing gas is 0.1 or more.

15. The substrate processing method of claim 14 , wherein the value of the ratio is 0.7 or less.

16. The substrate processing method according to any one of claims 11 to 15, further comprising alternately repeating the steps (b-1) and (b-2).

17. The Lewis acid gas is BX ３ , AlX ３ , FeX ３ , GaX ３ , SbX ５ , InX ３ , S.O. ２ , and SO ３ wherein X is F, Cl, Br, I, H, R, or OR, R is a methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group, or tert-butyl group, and OR is a methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, or tert-butoxy group.

18. 18. The substrate processing method according to claim 11, wherein the developing gas contains at least one selected from the group consisting of HBr, HCl, and a carboxylic acid.

19. a chamber; a substrate support disposed within the chamber; a gas supply configured to supply a gas into the chamber; a controller configured to control the gas supply unit; Equipped with The control unit controls the gas supply unit to supply BCl 3 to the substrate support unit while the substrate is placed on the substrate support unit and has a metal-containing film including an exposed first region and an unexposed second region. ３ and exposing the substrate to a gas and a HBr gas to selectively remove the second region relative to the first region and form a recess in the metal-containing film; the first region includes a high exposure region and a medium exposure region; the intermediate exposure region is located between the high exposure region and the second region and is exposed with an exposure amount less than that of the high exposure region; the step includes forming a protective portion on the surface of the intermediate exposure region exposed by forming the recess, the protective portion preventing the intermediate exposure region from coming into contact with the HBr gas. Substrate processing system.

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