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

Substrate processing method and substrate processing system

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

[0002] Japanese Patent Application Laid-Open No. 2003-124222 discloses a technique for forming a thin film that is patterned on a semiconductor substrate using extreme ultraviolet light (hereinafter referred to as "EUV").

[0003] Special Publication No. 2021-523403

[0004] The present disclosure provides techniques for properly developing metal-containing films.

[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. The method further includes (b) treating the substrate with BCl. ３ and HBr gas to selectively remove the second region relative to the first region to form a recess in the metal-containing film.

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

[0007] 8A is a diagram illustrating an example of the configuration of a heat treatment system. FIG. 8B is a diagram illustrating an example of the configuration of a plasma treatment system. FIG. 8C is a diagram illustrating an example of the configuration of a capacitively coupled plasma treatment apparatus. FIG. 8D is a flowchart illustrating a substrate treatment method according to a first embodiment. FIG. 8E is a diagram illustrating an example of a cross-sectional structure of a substrate W provided in step ST11 of the substrate treatment method shown in FIG. 8F is a diagram illustrating an example of an undercoat film UF of a substrate W. FIG. 8F is a diagram illustrating an example of an undercoat film UF of a substrate W. FIG. 8A is a diagram illustrating the top surface (plan) and cross section of a metal-containing film MF after exposure, and FIG. 8B is a diagram illustrating the top surface (plan) and cross section of a metal-containing film MF developed using a conventional developing gas. FIG. 9A is a cross-sectional view of an example substrate including a protective portion, and FIG. 9B is a diagram illustrating the effect of the protective portion in one embodiment. FIG. 9C is a diagram illustrating an example of the cross-sectional structure of a substrate W after development. FIG. 11A is a schematic cross-sectional view illustrating another example of the configuration of a heat treatment system, and FIG. 11B is a schematic plan view illustrating another example of the configuration of a heat treatment system. FIG. 11C is a schematic view illustrating an example of the configuration of a substrate support. FIG. 11D is a flowchart illustrating a method MT2. 16 is a block diagram for explaining an example of the configuration of a substrate processing system SS. FIG. 16 is a flowchart showing a method MT. (a) and (b) of FIG. 16 are timing charts of an example of a development process performed according to either method MT1 or method MT2. FIG. 16 is a timing chart of an example of a development process performed according to method MT2. FIG. 16 is a graph showing the results of a first experiment. FIG. 16 is a graph showing the results of a second experiment. FIG. 16 is a graph showing the results of a third experiment.

[0008] According to one exemplary embodiment of the present disclosure, a method for processing a substrate includes the steps of: (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) treating the substrate 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.

[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 sidewall heater 104 is provided on the sidewall 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 a substrate W is placed. The substrate support 121 is formed, for example, in a circular shape in a plan view, and the substrate W is placed 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 placed on the substrate support 121. A ring assembly (not shown) may be arranged on the substrate support 121 to surround the substrate W. The ring assembly may include one or more annular members. By arranging the ring assembly around the substrate W, temperature controllability in the outer peripheral region of the substrate W can be improved. The ring assembly may be made of an inorganic material or an organic material depending on the desired thermal treatment.

[0014] The substrate support 121 is supported in 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) is formed in the sidewall of the processing chamber 102 at a position different from the position where the exhaust port 131 opens, so as to be able to be opened and closed freely.

[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 a 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 opening 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 pipe heater 160 for heating the gas in the gas supply pipe 152 is provided around the gas supply pipe 152. The gas supply pipe 152 is connected to a gas supply unit 170. The gas supply unit 170 includes at least one gas source and at least one flow rate controller. The gas supply unit may include a vaporizer that vaporizes a material in a liquid state.

[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 realized, 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), a HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 may communicate with the heat treatment apparatus 100 via a communication line such as a LAN (Local Area Network).

[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 generators may be used, including alternating current (AC) plasma generators and direct current (DC) plasma generators. In one embodiment, the AC signal (AC power) used in the AC plasma generator has a frequency in the range of 100 kHz to 10 GHz. Thus, AC signals include radio frequency (RF) signals and microwave signals. 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, part or all of the control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 is realized by, for example, a computer 2a. The control unit 2 may include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. Each 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. Furthermore, 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 process 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 process gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the multiple gas inlets 13c. The showerhead 13 also includes at least one upper electrode. In addition to the showerhead 13, the gas inlet 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, thereby attracting ion components in the formed plasma 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 generator 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 within a range of 100 kHz to 60 MHz. In one embodiment, the second RF generator 31b may be configured to generate multiple bias RF signals having different frequencies. The generated one or more bias RF signals are 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 the 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 the at least one upper electrode and configured to generate a second DC signal. The generated second DC signal is applied to the at least one 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 pulse waveform. In one embodiment, a waveform generator for generating the 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 in the plasma processing space 10s is regulated by the pressure regulating valve. 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. After step ST12, method MT1 may include a step ST13 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 thermal processing system (see FIG. 1). The method MT1 will be described below using an example in which the control unit 200 controls each unit of the thermal processing apparatus 100 to apply the method MT1 to a substrate W.

[0044] (Step ST11: Providing a substrate)

[0045] First, in step ST11, a substrate W is provided in the processing chamber 102 of the thermal processing apparatus 100. The substrate W is provided on the substrate support 121 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 may contain Sn and 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 the second film UF2 and the 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 antireflective 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 alternatingly stacked silicon oxide films and silicon nitride films. Alternatively, the third film UF3 may be composed of alternatingly stacked silicon oxide films and polycrystalline silicon films. Alternatively, the third film UF3 may be a stacked film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. The third film UF3 may be made of a stack of a silicon oxide film and a silicon carbonitride film, or may be a stacked 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 an adhesion improvement process or the like. 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 the photoresist film is irradiated with EUV light through an exposure mask (reticle). This forms a substrate W having an underlayer film UF and a metal-containing 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 is a region corresponding to a pattern (non-aperture region) that blocks EUV light and is provided on an exposure mask (reticle). EUV has a wavelength in the range of 10 nm to 20 nm, for example. EUV may have a wavelength in the range of 11 nm to 14 nm, and in one example has a wavelength of 13.5 nm. After exposure, the substrate W is transported from the exposure apparatus to a thermal treatment apparatus under atmosphere control and subjected to a thermal treatment, i.e., post-exposure bake (PEB). The substrate W after PEB may be subjected to an additional thermal 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. 8A, the first region MF1 of the metal-containing film MF may include a high exposure region EX1 and an intermediate exposure region EX2. The high exposure region EX1 is a region at or near the center of the first region MF1, where the exposure dose is sufficient. That is, the high exposure region EX1 is a region irradiated with a sufficient amount of light during exposure of the substrate W. On the other hand, the intermediate exposure region EX2 is a region closer to the second region MF2 than the high exposure region EX1, where the exposure dose is insufficient. That is, the intermediate exposure region EX2 is a region irradiated with an insufficient amount of light during exposure of the substrate W. Because developing gases such as HBr gas have high reactivity, when using developing gases such as HBr gas, 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. Therefore, when developing the metal-containing film MF 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, resulting in a reverse tapered cross-sectional shape.

[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. 9A, the surface of the first region MF1 (intermediate exposure 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 sidewalls that define the recess formed in step ST12. FIG. 9B is a diagram for explaining the effect of the protective portion PF in one embodiment. FIG. 9B shows a case where BCl is used as the gas containing Lewis acid. ３9B, the surface of the first region MF1 exposed by the dry development has Sn—O bonds, and BCl ３ Upon contact with the HBr gas, an O-B bond is formed, inhibiting contact between the surface of the first region MF1 and the HBr gas. That is, the protective portion containing boron or the region containing a bond between boron and oxygen inhibits contact between the surface of the first region MF1 and the 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, according to step ST12, the shape of the sidewall of the first region MF1 can be made closer to a vertical shape. Furthermore, according to step ST12, the reduction in the dimension (line width) of the first region MF1 due to development can be suppressed. As a result, according to method MT1, the exposure dose required to obtain the desired dimension (e.g., line width) can be reduced. That is, according to method MT1, the sensitivity can be improved. Furthermore, according to the 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 is, for example, BX ３ , AlX ３ , FeX ３ , GaX ３ , SbX ５ , InX ３ , S.O. ２ and SO ３and may contain at least one selected from the group consisting of: wherein 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. Furthermore, 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. Furthermore, 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, BCl is used as the gas containing a Lewis acid. ３ In step ST12 of this example, BCl gas can be used as the developing gas. ３ The gas and HBr gas may be supplied simultaneously.

[0057] In one embodiment, the flow rate of the gas containing Lewis acid in the processing gas may be less than the flow rate of the developing gas. For example, the processing gas may contain BCl ３ When BCl gas and HBr gas are used, the ratio of BCl gas to the flow rate of HBr gas is ３ The ratio of the flow rates of the gases may be controlled in the range of 0.1 to 0.7. ３ When the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of the developing gas is 0.1 or more, 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 less, development defects such as deterioration of roughness and / or scum can be sufficiently suppressed. Note that, during the period in which step ST12 is being performed, 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 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 predetermined temperature during the process ST12. For example, the process gas may be BCl 2 . ３When the HBr gas and the HBr gas are used, the temperature of the substrate support member 121 may be controlled to 120° C. or less or 100° C. or less during the period in which step ST12 is performed. If the temperature of the substrate support member 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 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 a step ST13 in which it is determined whether the substrate W after the 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 the step ST12. If it is determined in the step ST13 that the predetermined condition is not satisfied (if the result of the determination in the step ST13 in FIG. 4 is "NO"), the step ST12 may be performed again. On the other hand, if it is determined in the step ST13 that the predetermined condition is satisfied (if the result of the determination in the 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. 1A 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 nozzles 141b1, and the second gas nozzles 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 nozzles 141b1, and the second gas nozzles 141b2 may be the same or different. Heaters (not shown) may be disposed on the substrate support 121 and the sidewalls of the processing chamber 102, similar to those in 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 thermal processing apparatus 100a, the gas density in the processing chamber 102 can be easily controlled, and the in-plane uniformity in the development of the 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 perpendicular 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 enable 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 the 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), parts inside the processing chamber 102, such as the sidewall of the processing chamber 102 and / or the substrate support 121 (hereinafter also referred to as "chamber parts"), may be pre-coated. The pre-coating may be performed by atomic layer deposition (hereinafter also referred to as "ALD"), chemical vapor deposition (hereinafter also referred to as "CVD"), or the like. As a gas for forming the pre-coated film, a gas capable of forming a film resistant to a processing gas containing at least one selected from the group consisting of HBr, HCl, carboxylic acid, and Lewis acid gas may be selected. Note that the Lewis acid gas may be BX, as described above. ３ , AlX ３ , FeX ３ , GaX ３, SbX ５ , InX ３ , S.O. ２ , and SO ３ The gas for forming the pre-coat film may include at least one selected from the group consisting of: aminosilane or SiCl ４ In this case, a silicon oxide film can be formed as a pre-coat film on the sidewall of the processing chamber 102 and / or the parts inside the chamber, thereby suppressing corrosion of the sidewall of the processing chamber 102 and / or the substrate support 121, etc., caused by the processing gas.

[0070] Alternatively, instead of or in addition to the pre-coating, the sidewalls and / or parts inside the process chamber 102 may be made of a material that is 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. As described above, the Lewis acid gas is BX. ３ , AlX ３ , FeX ３ , GaX ３ , SbX ５ , InX ３ , S.O. ２ , and SO ３ It may contain at least one selected from the group consisting of:

[0071] In the substrate processing method of the present disclosure, the inside of 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 to perform cleaning by heat. For example, the processing chamber 102 and the parts inside the chamber may be heated before supplying cleaning gas into the processing chamber 102. Alternatively, cleaning gas may be supplied into the processing chamber 102 to perform cleaning by plasma generated from the cleaning gas. The cleaning gas may be H ２ , HBr, HCl, BCl ３ , Cl ２ , C.H. ３ OH, C ２ H ５ OH and CH ４and O ２ and the like, and may contain at least one of Ar and / or N ２ 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 metal oxides adhering to the sidewalls and / or parts inside the processing chamber 102 during development to be removed.

[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, etc. In one embodiment, the etching of the base film UF may be performed by the plasma processing apparatus 1 shown in FIG.

[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 in the same manner as in step ST11. The substrate may be the same as the 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 a gas containing a Lewis acid is supplied into the process chamber 102 before the developing gas, and then the developing gas is supplied. Note that the second process gas may further contain a gas containing a Lewis acid. Method MT2 may also include a 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 also be the same as the developing gas in method MT1.

[0077] The flow rate of the gas containing Lewis acid in the second process gas may be lower than the flow rate of the developing gas. For example, the second process gas may contain BCl ３ When BCl gas and HBr gas are used, the ratio of the flow rate of BCl to the flow rate of HBr gas in the second process gas is ３ The ratio of the flow rates of the gases may be controlled to a value in the range of 0.1 to 0.7. ３ When the ratio of the flow rate of the gas containing a Lewis acid to the flow rate of the developing gas is 0.1 or more, 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 less, development defects such as deterioration of roughness and / or scum can be sufficiently suppressed. Note that, during the period in which step ST23 is being performed, 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 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 process 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 process 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, the first process gas may be BCl 2 . ３ gas, and BCl as the second process gas. ３When using HBr gas and HBr gas, the temperature of the substrate support 121 may be controlled to 120°C or less or 100°C or less during the period when steps ST22 and ST23 are 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 be highly vertical, and a reduction in the dimension (line width) of the first region MF1 due to development can be suppressed. As a result, method MT2 can reduce the exposure dose required to obtain the desired dimension (e.g., line width). 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 length of the processing time of process ST22 may be shorter than the length of the processing time of process ST23. In one example, the ratio of the length of the processing time of process ST22 to the length of the processing time of process ST23 may be controlled to 0.5 or less or 0.3 or less. If the ratio of the length of the processing time of process ST22 to the length of the processing time of process 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 a step ST24 in which it is determined whether the substrate W after the 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 the steps ST22 and ST23. If it is determined in the step ST24 that the predetermined condition is not satisfied (if the result of the determination in the step ST24 in FIG. 13 is "NO"), the step ST22 may be performed again. On the other hand, if it is determined in the step ST24 that the predetermined condition is satisfied (if the result of the determination in the step ST24 in FIG. 13 is "YES"), the method MT2 may be terminated.

[0084] <Configuration example of substrate processing system>

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

[0086] The first carrier station CS1 transfers 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 substrates 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 substrates W between the first carrier C1 on each first loading tray 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 internal pressure of the first transport device HD1. The "vacuum" refers to a pressure lower than atmospheric pressure, and may be, for example, a medium vacuum of 0.1 Pa to 100 Pa. The interior of the second transport device HD2 may be atmospheric pressure or a vacuum. The load lock module may be used, for example, to transport 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 also to transport 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 substrates W. In one embodiment, the first processing station PS1 includes a pre-processing module PM1, a resist film formation 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 transport device HD2 that transports the substrates W. The second transport device HD2 transports and transfers the substrates 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-treatment module PM1, the substrate W is subjected to pre-treatment. In one embodiment, the pre-treatment 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, etc. In one embodiment, the pre-treatment module PM1 includes a surface modification treatment unit that performs a surface modification treatment on the substrate W. Each treatment unit in the pre-treatment module PM1 may be configured to include a heat treatment apparatus 100 (see FIG. 1) and a plasma treatment apparatus 1 (see FIGS. 2 and 3).

[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 formation 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 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 transport device HD3. The third transport device HD3 transports and transfers substrates W between the first processing station PS1 and the exposure apparatus EX. The third transport device HD3 has a housing that accommodates 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 transfers 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 substrates 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 transport device HD5 that transports the substrates W. The fifth transport device HD5 transports and transfers the substrates 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 table on which the substrate W is placed, an imaging device, an illumination device, and various sensors (temperature sensor, reflectance measurement sensor, etc.). The imaging device may be, for example, a CCD camera that 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, the thermal processing apparatus 100 (see FIG. 1) or the 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 developed 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.

[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 controller CT controls each component of the substrate processing system SS to perform a given process on the substrate W. The controller CT stores a recipe in which a process procedure, process conditions, transport conditions, etc. are set, and controls each component of the substrate processing system SS to perform a given process on the substrate W in accordance with the recipe. The controller CT may also have some or all of the functions of the controllers (controller 200 and controller 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 a process ST100 for pre-treating a substrate, a process ST200 for forming a resist film on the substrate, a process ST300 for performing a heat treatment (pre-bake: PAB) on the substrate on which the resist film has been formed, a process ST400 for exposing the substrate to EUV light, a process ST500 for performing a heat treatment (post-exposure bake: PEB) on the exposed substrate, a process ST600 for measuring the substrate, a process ST700 for developing the resist film on the substrate, a process ST800 for performing a heat treatment (post-bake: PB) on the developed substrate, and a process ST900 for etching the substrate. Method MT may not include one or more of the above processes. For example, method MT may not include process ST600, and process ST700 may be performed after process ST500.

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

[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 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 on 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) for removing the resist film from the edge of the substrate W may be performed.

[0114] (Step ST400: EUV exposure)

[0115] Next, the substrate W is transferred by the second transport device HD2 to the third transport device HD3 of the first interface station IS1. The substrate W is then transported by the third transport 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 transport device HD4 in the second interface station IS2 to the fifth transport device HD5 in the second processing station PS2. The substrate W is then transported by the fifth transport 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. Alternatively, the post-exposure bake may 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 controller 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 controller 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 of the resist film and the surface of the base 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 base 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 transported by the fifth transport device HD5 to the third thermal treatment module PM7, where it is subjected to a thermal treatment (post-baking). The post-baking may be performed in an air atmosphere, or in an N ２ Or O ２The post-baking may be performed in a reduced pressure atmosphere containing . Furthermore, the post-baking may be performed by heating the substrate W to 150° C. or higher and 250° C. or lower. The post-baking may be performed in the second thermal treatment module PM4 instead of the third thermal treatment module PM7. In one embodiment, after the post-baking, the measurement module PM5 may perform optical measurement of the substrate W. Such measurement may be performed in addition to or instead of the measurement in process ST600. In one embodiment, the controller CT determines the presence or absence of an abnormality, such as a defect, a scratch, or foreign matter adhesion, 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 an abnormality exists, the substrate W may be reworked or discarded without being etched in process ST900. In one embodiment, if the controller CT determines that an abnormality exists, the opening dimensions of the resist film on the substrate W may be adjusted using a dry coating unit (such as a CVD apparatus or an ALD apparatus).

[0125] (Step ST900: Etching)

[0126] After the process ST800 is performed, the substrate W is transferred by the fifth transport device HD5 to the sixth transport device HD6 of the second carrier station CS2, and then transferred by the sixth transport device HD6 to the second carrier C2 of the second mounting tray ST2. The second carrier C2 is then transferred to a plasma processing system (not shown). In the plasma processing system, the base film UF of the substrate W is etched using the developed resist film as a mask. This completes the method MT. Note that, when the resist film is developed using a plasma processing device in the process ST700, etching may be performed subsequently in a plasma processing chamber of the plasma processing device. Furthermore, if the second processing station PS2 includes a plasma processing module in addition to the developing module PM6, etching may be performed in the plasma processing module. 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] 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, although the supply of the Lewis acid gas and the supply of the developing gas are stopped simultaneously in the examples shown in each of FIGS. 16(a) and 16(b), the supply of the Lewis acid gas and 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 step ST22 and step 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 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 flow rate D2. Meanwhile, the flow rate of the Lewis acid gas in step ST23 is set to L1. Flow rate L1 is smaller than flow rate L2. Flow rate L1 may be zero or greater than zero. Furthermore, flow rate D1 is smaller than flow rate D2. 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, flow rate L2 and / or flow rate D2 may be changed depending on the elapsed time of the development process. For example, as the development process progresses, flow rate D2 may be reduced to a value smaller than flow rate L2.

[0131] As shown in FIG. 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, adjusting 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 the periods of step ST22 and step ST23, or may partially overlap them.

[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 process gas. The metal-containing film was a resist film containing tin oxide. Two process gases were used separately. One of the two process gases contained only HBr gas, and the other contained HBr gas and BCl. ３ The processing gas was a processing gas containing a metal-containing film. Then, the film thickness of the metal-containing film after processing using the processing gas, that is, the remaining film amount, was measured.

[0136] The results of the first experiment are shown in FIG. 19. In the graph of FIG. 19, the horizontal axis represents the exposure dose, and the vertical axis represents the remaining film amount (Film Remain) 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 & BCl ３ " is HBr gas and BCl ３ As shown in FIG. 19, the results are shown for the case where a process gas containing HBr gas and BCl gas was used. ３ The residual film amount when the processing gas containing HBr gas was used was larger than the residual film amount when the processing gas containing only HBr gas was used. ３ It has been confirmed that the sensitivity is improved by using a process gas containing a developing gas and a Lewis acid gas.

[0137] (Second Experiment)

[0138] In a second 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. Two separate process gases were used. One of the two process gases contained only HBr gas, and the other contained HBr gas and BCl gas. ３ The process gas contained HBr gas and BCl３ In the process gas containing HBr gas, the ratio of the flow rates (flow rate of HBr gas: BCl ３ The ratio of the flow rate of the processing gas to the flow rate of the metal-containing film was 10:1. Then, the film thickness of the metal-containing film after the processing using the processing gas, that is, the remaining film amount, was measured.

[0139] The results of the second experiment are shown in FIG. 20. In the graph of FIG. 20, the horizontal axis represents the exposure dose, and the vertical axis represents the remaining film amount (Film Remain) of the metal-containing film after processing using the processing gas. In the graph of FIG. 20, "HBr Only" represents the results when a processing gas containing only HBr gas was used. "HBr:BCl ３ = 10: 1 (BCl ３ "First addition" is BCl ３ First, HBr gas and BCl ３ The results are shown for the case where a process gas containing HBr:BCl was supplied. ３ = 10: 1 (BCl ３ "Simultaneous addition" refers to the simultaneous supply of HBr gas and BCl ３ The results are shown for the case where the gas supply was started simultaneously. ３ = 10: 1 (BCl ３ "Post-addition" refers to the process in which only HBr gas is supplied, and then HBr gas and BCl ３ As shown in FIG. 20, the results are shown for a case where a process gas containing BCl ３ When BCl gas is supplied before HBr gas, and when BCl gas is supplied after HBr gas, ３ When the gas supply was started simultaneously, the remaining film amount was larger than the remaining film amount in the other cases. ３ The gas is supplied before the HBr gas, or the HBr gas and the BCl ３ It was confirmed that the sensitivity was improved by starting the supply of the gases simultaneously, that is, by starting the supply of the Lewis acid gas before the supply of the developing gas, or by starting the supply of the developing gas and the supply of the Lewis acid gas simultaneously.

[0140] (Third Experiment)

[0141] In a 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 process gases were used individually. The first of the four process gases was HBr gas and BCl gas. ３ The ratio of the flow rates of the first gas (HBr gas flow rate: BCl ３ The ratio of the flow rate of the gases was 10:7. The second gas among the four processing gases was HBr gas and BCl ３ The ratio of the flow rates of the first and second gases (HBr gas flow rate: BCl ３ The ratio of the flow rate of the gases was 10:4. The third gas among the four process gases was HBr gas and BCl ３ and the ratio of the flow rates of the third gas (HBr gas flow rate: BCl ３ The ratio of the flow rate of the gases was 10:1. The fourth gas among the four processing gases was a processing gas containing only HBr gas. Then, the film thickness of the metal-containing film after processing using the processing gas, i.e., 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 (Film Remain) of the metal-containing film after processing using the processing gas. ３ =10:7”, “HBr:BCl ３ =10:4”, “HBr:BCl ３ =10:1”, “HBr:BCl ３ = 10:0 (HBr Only)" indicates the results when the first to fourth gases were used, respectively. As shown in FIG. 21, when the flow rate ratio was 10:7, 10:4, or 10:1, the residual film amount was greater than the residual film amount when a processing gas containing only HBr gas was used. From this result, it can be seen that the ratio of BCl to the flow rate of HBr gas ３ It was confirmed that high sensitivity was obtained when the gas flow rate ratio was in the range of 0.1 to 0.7.

[0143] (Fourth Experiment)

[0144] In a fourth 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 process gas. The metal-containing film was a resist film containing tin oxide. Two process gases were used separately. One of the two process gases contained only HBr gas, and the other contained HBr gas and BCl. ３ The process gas contained HBr gas and BCl gas. The difference ΔCD between the maximum width and the minimum width in the cross section of the line portion in the line and space pattern was calculated. ３ The difference ΔCD when using a process gas containing HBr gas was normalized by the difference ΔCD when using a process gas containing only HBr gas to obtain a value ΔCDn. The result was 0.78. From this result, it can be seen that the difference ΔCD when using a process gas containing HBr gas and BCl ３ It has been confirmed that by using a process gas containing a Lewis acid gas and a developing gas, it is possible to obtain the first region MF1 having high verticality.

[0145] (Fifth 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 process gas. The metal-containing film was a resist film containing tin oxide. Four process gases were used individually. The first of the four process gases was HBr gas and O ２ The second of the four treatment gases was HBr gas and SO ２ The third gas among the four processing gases was HBr gas and BCl ３ The fourth gas among the four types of process gases was a gas containing only HBr gas. When each of the four types of process gases was used, the exposure dose (mJ / cm) required to form a line and space pattern including a line portion having a line width of 16 nm was calculated. ２) was identified. Then, 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 used 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 the sensitivity was improved by using HBr gas and BCl gas. ３ It was confirmed that roughness was improved by using a processing gas containing the gas.

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

[0148] [E1] (a) providing a substrate on a substrate support in a chamber, the substrate having a metal-containing film including first exposed regions and second unexposed regions; (b) treating the substrate 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, thereby forming a recess in the metal-containing film.

[0149] [E2] The substrate processing method according to E1, wherein in (b), the temperature of the substrate support part 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 defining the recess.

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

[0152] [E5] (b) is a step of dissolving the BCl ３The substrate processing method of any one of E1 to E4, further comprising simultaneously supplying the HBr gas and the HBr gas.

[0153] [E6] The (b) is: (b-1) supplying the BCl 3 gas into the chamber before supplying the HBr gas. ３ (b-2) supplying the HBr gas after (b-1).

[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 flow rate of the HBr gas is ３ The substrate processing method according to any one of E1 to E7, wherein the flow rate of the gas is greater than the flow rate of the gas.

[0156] [E9] The ratio of the BCl to the flow rate of the HBr gas ３ The substrate processing method according to any one of E1 to E7, wherein the ratio of the gas flow rates 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 substrate processing method comprising: (a) providing a substrate on a substrate support in a chamber, the substrate having a metal-containing film including a first region that is exposed and a second region that is unexposed; and (b) selectively removing the second region relative to the first region to form a recess in the metal-containing film, wherein (b) comprises: (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 including a developer gas for a second period of time; and wherein the second period of time starts at or after the start of the first period of time.

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

[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, comprising alternately repeating (b-1) and (b-2).

[0164] [E17] 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, 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.

[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 method for manufacturing a semiconductor device, comprising: a chamber; a substrate support provided in the chamber; a gas supply unit configured to supply a gas into the chamber; and a control unit configured to control the gas supply unit, wherein the control unit controls a gas supply unit to supply BCl from the gas supply unit while a substrate having a metal-containing film including an exposed first region and an unexposed second region is placed on the substrate support unit. ３ and exposing the substrate to a gas and HBr gas to selectively remove the second region relative to the first region and form a recess in the metal-containing film.

[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.

[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) A step of providing a substrate on a substrate support portion in a chamber, the substrate having a metal-containing film including an exposed first region and an unexposed second region; and (b) exposing the substrate to BCl ３ gas and HBr gas to selectively remove the second region with respect to the first region and form a recess in the metal-containing film; A substrate processing method including the above.

2. The substrate processing method according to claim 1, wherein in (b) above, the temperature of the substrate support portion is set to a temperature of 100°C or lower.

3. The substrate processing method according to claim 1, wherein in (b) above, a protective portion containing boron is formed on the side wall defining the recess.

4. The substrate processing method according to claim 1, wherein in (b) above, a bond of boron and oxygen is formed on the side wall defining the recess.

5. The first region includes a high-exposure region and an intermediate-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, In (b) above, the temperature of the substrate support portion is set to a temperature of 100°C or lower, (b) includes forming a protective portion on the surface of the intermediate-exposure region exposed by forming the recess to inhibit contact between the intermediate-exposure region and the HBr gas. The substrate processing method according to any one of claims 1 to 4.

6. The substrate processing method according to claim 5, wherein the protective portion is formed by bonding boron contained in the BCl 3 gas and oxygen in the metal-containing film.

7. The above (b) includes simultaneously supplying the BCl ３ gas and the HBr gas into the chamber. The substrate processing method according to any one of claims 1 to 4.

8. In (b) above, (b-1) Before supplying the HBr gas, supply the BCl gas into the chamber, and ３ and (b-2) After (b-1), supplying the HBr gas; The substrate processing method according to any one of claims 1 to 4, including the above.

9. The substrate processing method according to claim 8, wherein the length of the time during which (b-1) is performed is shorter than the length of the time during which (b-2) is performed.

10. The flow rate of the HBr gas is higher than the flow rate of the BCl ３ gas, and the substrate processing method according to any one of claims 1 to 4.

11. The ratio of the flow rate of the BCl ３ gas to the flow rate of the HBr gas is 0.1 or more. The substrate processing method according to any one of claims 1 to 4.

12. The substrate processing method according to claim 11, wherein the value of the ratio is 0.7 or less.

13. The substrate processing method according to any one of claims 1 to 4, wherein the metal-containing film includes at least one selected from the group consisting of tin, hafnium, and titanium.

14. (a) A step of providing a substrate on a substrate support portion in a chamber, the substrate having a metal-containing film including an exposed first region and an unexposed second region; and (b) A step of selectively removing the second region with respect to the first region to form a recess in the metal-containing film; and including In (b) above, (b-1) exposing the substrate to a first processing gas containing a Lewis acid gas during a first period, and (b-2) exposing the substrate to a second processing gas containing a developing gas during a second period, comprising: the second period starts at or after the start time of the first period, Substrate processing method. the second processing gas further contains the Lewis acid gas, in the second period, the flow rate of the developing gas is greater than the flow rate of the Lewis acid gas, the substrate processing method according to claim 14. the value of the ratio of the flow rate of the Lewis acid gas to the flow rate of the developing gas is 0.1 or more, the substrate processing method according to claim 14. the value of the ratio is 0.7 or less, the substrate processing method according to claim 16. including alternately repeating (b-1) and (b-2), the substrate processing method according to any one of claims 14 to 17. the developing gas contains at least one selected from the group consisting of HBr, HCl, and carboxylic acid, the substrate processing method according to any one of claims 14 to 17 and 19. a chamber, a substrate support provided in the chamber, a gas supply unit configured to supply gas into the chamber, a control unit configured to control the gas supply unit, The Lewis acid gas is BX ３ , AlX ３ , FeX ３ , GaX ３ , SbX ５ , InX ３ , SO ２ , and SO ３ and includes at least one selected from the group consisting of, where X is F, Cl, Br, I, H, R, or OR, where 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, the substrate processing method according to claim 14. comprising: Substrate processing system. ​ ​ ​ ​ ​ ​ In a state where a substrate having a metal-containing film including an exposed first region and an unexposed second region is placed on the substrate support unit, the control unit exposes the substrate to BCl ３ gas and HBr gas to selectively remove the second region with respect to the first region and form a recess in the metal-containing film. ​