Substrate processing method and substrate processing apparatus

Abstract

In one exemplary embodiment of the present invention, a substrate processing method includes: (a) a step of processing a substrate in a chamber, in which a metal-containing material is formed on the surface of at least one among the chamber, the substrate, and a component that is disposed in the chamber by processing the substrate; and (b) a step for replacing a metal contained in the metal-containing material with silicon by supplying a first processing gas that contains a silicon-containing gas into the chamber after the step (a).

Description

Substrate processing method and substrate processing apparatus

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

[0002] Japanese Patent Application Laid-Open No. 2003-144222 discloses a method of etching a laminated film of an aluminum film and a titanium nitride film, and then cleaning the laminated film by converting a mixed gas of boron trichloride and chlorine into plasma.

[0003] Japanese Patent Application Laid-Open No. 2000-12515

[0004] The present disclosure provides techniques that can reduce contamination of the chamber, the substrate, or components disposed within the chamber.

[0005] In one exemplary embodiment, a substrate processing method includes: (a) processing a substrate in a chamber, whereby a metal-containing material is formed on at least one surface of the chamber, the substrate, or a component disposed in the chamber; and (b) after (a), supplying a first process gas containing a silicon-containing gas into the chamber to replace metal contained in the metal-containing material with silicon.

[0006] According to one exemplary embodiment, a technique is provided that can reduce contamination of a chamber, a substrate, or a component disposed within the chamber.

[0007] FIG. 1 is a diagram illustrating an example of the configuration of a thermal processing system. FIG. 2 is a diagram schematically illustrating a substrate processing apparatus according to another exemplary embodiment. FIG. 3 is a diagram schematically illustrating a substrate processing apparatus according to another exemplary embodiment. FIG. 4 is a flowchart of a substrate processing method according to an exemplary embodiment. FIG. 5 is a partially enlarged cross-sectional view illustrating an example of a processing chamber when a pre-coat film is coated. FIG. 6 is a diagram illustrating an example of a structural formula of an aminosilane. FIG. 7 is a cross-sectional view illustrating an example of a first substrate to which the method illustrated in FIG. 4 can be applied. FIG. 8 is a cross-sectional view illustrating an example of a first substrate after a metal-containing film has been formed on an underlayer film of the first substrate. FIG. 9 is a cross-sectional view illustrating an example of a first substrate after a metal-containing resist has been formed by exposing the metal-containing film. FIG. 10 is a cross-sectional view illustrating an example of a first substrate after a developing gas has been supplied to remove a second region. FIG. 11 is a cross-sectional view illustrating an example of a first substrate after an etching gas has been supplied to etch the underlayer film. FIG. 12 is a partially enlarged cross-sectional view illustrating an example of a processing chamber when a second substrate is provided into the processing chamber. FIG. 13 is a partially enlarged cross-sectional view showing an example of a processing chamber when a first processing gas is supplied to replace the metal contained in the metal-containing material with silicon. FIG. 14 is a partially enlarged cross-sectional view showing an example of a processing chamber when a second processing gas is supplied to remove the silicon-containing material. FIG. 15 is a partially enlarged cross-sectional view showing an example of a processing chamber when a third processing gas is supplied to coat a silicon-containing film on the surface of the processing chamber or a component. FIG. 16 is another flowchart of a substrate processing method according to an illustrative embodiment. FIG. 17 is a flowchart of a substrate processing method according to a modified example. FIG. 18 is a schematic diagram of an example of a processing chamber when a first processing gas is supplied to replace the metal contained in the metal-containing material attached to a first substrate with silicon. FIG. 19 is a schematic diagram of another example of a chamber when a first processing gas is supplied to replace the metal contained in the metal-containing material attached to a first substrate with silicon.

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

[0009] 1 is a diagram illustrating an example of the configuration of a heat treatment system. In one exemplary 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. The heat treatment apparatus 100 is an example of a substrate treatment apparatus.

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

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

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

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

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

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

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

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

[0018] The control unit 200 processes computer-executable instructions that cause the heat treatment apparatus 100 to perform the various steps described in this disclosure. The control unit 200 may be configured to control each element of the heat treatment apparatus 100 to perform the various steps described herein. In one embodiment, part or all of the control unit 200 may be included in the heat treatment apparatus 100. The control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3. The control unit 200 is 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).

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

[0020] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma generated 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.

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

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

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

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

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

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

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

[0028] The showerhead 13 is configured to introduce at least one 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.

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

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

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

[0032] The second RF 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 in the 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.

[0033] The power supply 30 may include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generator 32a and a second DC generator 32b. In one embodiment, the first DC generator 32a is connected to 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.

[0034] In various embodiments, the first and second DC signals may be pulsed. In this case, a sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulses may have a rectangular, trapezoidal, triangular, or combination thereof 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.

[0035] The exhaust system 40 may be connected to, for example, a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure 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.

[0036] [Substrate Processing Method] FIG. 4 is a flowchart of a substrate processing method (hereinafter referred to as "method MT1") according to one example embodiment. As shown in FIG. 4, method MT1 may include steps ST11 to ST27. Steps ST11 to ST27 may be performed in order. In the following example, a series of processes including film formation, exposure, development, and etching will be described as an example of a substrate processing method. Method MT1 may include at least one of step ST13, step ST19, and step ST20, and step ST23, or may not include other steps.

[0037] The method MT1 may be performed using any one of the substrate processing systems described above (see FIGS. 1 to 3), or may be performed using two or more of these substrate processing systems. For example, the method MT1 may be performed using a thermal processing system (see FIG. 1). The following describes an example in which the control unit 200 controls each unit of the thermal processing apparatus 100 to perform the method MT1 on a first substrate W1 (see FIG. 6) and a second substrate W2 (see FIG. 11).

[0038] (Process ST11: Supplying Precoat Gas to Coat Precoat Film) First, in process ST11, as shown in FIG. 5 , a precoat gas GP containing a silicon-containing gas is supplied into the process chamber 102 to coat a precoat film MS1 on at least one surface of the process chamber 102 or a component disposed in the process chamber 102. The precoat film MS1 may be formed to completely cover at least one surface of the process chamber 102 or the component, or may be formed to partially cover at least one surface of the process chamber 102 or the component. Examples of components disposed in the process chamber 102 include the substrate support 121, the support pillars 122, and the ring assembly 125. FIG. 5 is a partially enlarged cross-sectional view showing an example of the process chamber 102 when coating the precoat film MS1. In the example of FIG. 5 , in process ST11, a precoat gas GP is supplied to coat the inner surface of the process chamber 102, the surface of the ring assembly 125, the surface of the support pillars 122, and the surface of the substrate support 121 with the precoat film MS1. In process ST11, a dummy wafer may be placed on the substrate support part 121, or a substrate may not be placed on the substrate support part 121. After completion of process ST11, the dummy wafer may be transported out of the processing chamber 102. By coating at least one surface of the processing chamber 102 or a component with the precoat film MS1, metals are less likely to adhere to the surface of the processing chamber 102 or the component during substrate processing, which will be described later. This makes it possible to suppress contamination of the processing chamber 102 or the component by metals.

[0039] The precoat gas GP may contain a silicon-containing gas. In this case, a silicon-containing film may be formed as the precoat film MS1. The precoat gas GP may contain a carbon-containing gas. In this case, a carbon-containing film may be formed as the precoat film MS1. The precoat gas GP may further contain an oxygen-containing gas. The precoat film MS1 may be formed by CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition).

[0040] When the precoat gas GP contains a silicon-containing gas, the silicon-containing gas may contain at least one selected from the group consisting of a gas containing silicon and chlorine, a gas containing silicon and bromine, a gas containing silicon and iodine, a gas containing silicon and hydrogen, and an aminosilane gas. The silicon-containing gas may further contain hydrogen, and may be dichlorosilane (SiH ２ Cl ２ The silicon and bromine containing gas may further include hydrogen, and may include dibromosilane (SiH ２ Br ２ The silicon and iodine-containing gas may further include hydrogen, and may include diiodosilane (SiH ２ I ２ The silicon and hydrogen containing gas may include monosilane (SiH ４ ) gas, disilane (Si ２ H ６ The aminosilane gas may have 1 to 4 amino groups.

[0041] 6 is a diagram showing an example of the structural formula of an aminosilane. １ ~R ８ and R ａ ~R ｃEach of the symbols represents hydrogen or a hydrocarbon. The hydrocarbon may contain nitrogen, oxygen, and halogen atoms. (a) of Figure 6 shows an aminosilane having one amino group. (b) of Figure 6 shows an aminosilane having two amino groups. (c) of Figure 6 shows an aminosilane having three amino groups. (d) of Figure 6 shows an aminosilane having four amino groups.

[0042] Examples of aminosilanes include butylaminosilane (BAS), bis(tertiarybutylaminosilane) (BTBAS), dimethylaminosilane (DMAS), bis(dimethylaminosilane) (BDMAS), tridimethylaminosilane (TDMAS), diethylaminosilane (DEAS), bis(diethylaminosilane) (BDEAS), dipropylaminosilane (DPAS), diisopropylaminosilane (DIPAS), hexakisethylaminodisilane, and silanes of the formula (1) ((R1R2)N) ｎ Si Ｘ H ２Ｘ＋２-ｎ-ｍ (R3) ｍ , and (2) formula ((R1R2)N) ｎ Si Ｘ H ２Ｘ-ｎ-ｍ (R3) ｍ Includes:

[0043] In the above formulas (1) and (2), n is the number of amino groups and is a natural number from 1 to 6. m is the number of alkyl groups and is 0 or a natural number from 1 to 5. R1, R2, or R3 is CH ３ , C ２ H ５ or C ３ H ７ R1, R2 and R3 may or may not be the same as each other. R3 may be Cl or F. X is a natural number of 1 or more.

[0044] (Step ST12: Providing the first substrate W1 into the processing chamber 102) Subsequently, in step ST12, the first substrate W1, whose inner surface is coated with the pre-coat film MS1, is provided into the processing chamber 102. The first substrate W1 is provided onto the substrate support 121 by, for example, lowering the lift pins 123.

[0045] 7 is a cross-sectional view showing an example of a first substrate W1 to which the method MT1 can be applied. The first substrate W1 includes an underlayer UF. The first substrate W1 may be used in the manufacture of semiconductor devices. The semiconductor devices include, for example, memory devices such as DRAMs and 3D-NAND flash memories, and logic devices.

[0046] The underlayer UF may be formed on a silicon wafer. The underlayer UF may be at least one selected from the group consisting of a carbon-containing film, a silicon nitride film, a silicon carbide film, and an amorphous silicon film. Examples of the carbon-containing film include an amorphous carbon film.

[0047] (Process ST13: Forming a metal-containing film MK on the base film UF of the first substrate W1) Subsequently, in process ST13, as shown in FIG. 8, a metal-containing film MK is formed on the base film UF of the first substrate W1. FIG. 8 is a cross-sectional view showing an example of the first substrate W1 after process ST13. In process ST13, the metal-containing film MK may be formed using a wet process such as a solution coating method.

[0048] The metal-containing film MK may be an EUV resist. The metal-containing film MK may contain tin (Sn) as a metal. The metal-containing film MK may contain at least one metal selected from the group consisting of tellurium (Te), antimony (Sb), indium (In), silver (Ag), titanium (Ti), chromium (Cr), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), germanium (Ge), and hafnium (Hf). The metal-containing film MK may further contain oxygen. The metal-containing film MK may contain, for example, tin oxide. The metal-containing film MK may further contain an organic substance such as an organic ligand.

[0049] Before the metal-containing film MK is formed, the base film UF may be subjected to a surface modification treatment. After the formation of the metal-containing film MK, the first substrate W1 may be subjected to a heat treatment, i.e., pre-baked (Post Apply Bake: PAB). After the pre-baking, an additional heat treatment may be performed.

[0050] (Step ST14: Transporting the first substrate W1 out of the processing chamber 102) Subsequently, in step ST14, the first substrate W1 is transported out of the processing chamber 102. For example, the heat treatment apparatus 100 may form a substrate processing system together with an exposure apparatus and a transport apparatus. In this case, the transport apparatus may transport the first substrate W1 out of the processing chamber 102.

[0051] (Step ST15: Providing the First Substrate W1 into the Exposure Apparatus) Then, in step ST15, the transport apparatus provides the first substrate W1 into the exposure apparatus.

[0052] (Step ST16: Exposing the Metal-Containing Film MK to Form a Metal-Containing Resist MF) Subsequently, in step ST16, as shown in FIG. 9 , the metal-containing film MK is exposed to form a metal-containing resist MF. The metal-containing resist MF may contain the same metal as the metal-containing film MK. FIG. 9 is a cross-sectional view showing an example of the first substrate W1 after step ST16. The exposure apparatus forms the metal-containing resist MF by exposing the metal-containing film MK on the substrate W using an exposure mask (reticle). As shown in FIG. 9 , the metal-containing resist MF has an exposed first region MF1 and an unexposed second region MF2. The first region MF1 may be an exposed region exposed by EUV. The second region MF2 may be an unexposed region not exposed by EUV. The exposure apparatus may be, for example, an EUV exposure apparatus using EUV as a light source.

[0053] The first region MF1 may be a region corresponding to an opening provided in an exposure mask (reticle). The second region MF2 may be a region corresponding to a pattern provided in the exposure mask (reticle). EUV has a wavelength in the range of 10 nm to 20 nm, for example. EUV may have a wavelength in the range of 11 nm to 14 nm, and in one example has a wavelength of 13.5 nm.

[0054] (Step ST17: Transporting the first substrate W1 out of the exposure apparatus) Subsequently, in step ST17, the first substrate W1 is transported out of the exposure apparatus. For example, a transport apparatus may transport the first substrate W1 out of the exposure apparatus. The first substrate W1 after exposure may be subjected to a heat treatment, i.e., post-exposure bake (PEB). The first substrate W1 after exposure may be further heated after the PEB.

[0055] (Process ST18: Providing the first substrate W1 into the processing chamber 102) Then, in process ST18, the transport device again provides the first substrate W1 into the processing chamber 102, whose inner surface is coated with the precoat film MS1 (see Figure 5).

[0056] After the first substrate W1 is placed on the substrate support 121, the temperature of the substrate support 121 is adjusted to a set temperature. The temperature adjustment of the substrate support 121 may be performed by controlling the output of one or more of the sidewall heater 104, the stage heater 120, the ceiling heater 130, or the piping heater 160. In the method MT1, the temperature of the substrate support 121 may be adjusted to the set temperature before step ST18. That is, the first substrate W1 may be provided on the substrate support 121 after the temperature of the substrate support 121 is adjusted to the set temperature.

[0057] (Process ST19: Supplying developing gas to remove second region MF2) Subsequently, in process ST19, as shown in FIG. 10, dry development is performed in which developing gas is supplied to remove the second region MF2. FIG. 10 is a cross-sectional view showing an example of the first substrate W1 after process ST19. In process ST19, the second region MF2 is removed by dry development by supplying developing gas into the processing chamber 102. Process ST13 may be performed until the base film UF is exposed. As a result, the first region MF1 is formed on the base film UF as a pattern after development. The pattern of the first region MF1 after development may be a line pattern or a dot pattern in a plan view of the first substrate W1.

[0058] The developing gas may include at least one of a hydrogen-containing gas and a bromine-containing gas. The developing gas may include a hydrogen bromide (HBr)-containing gas. The developing gas may include hydrogen fluoride (HF), hydrogen chloride (HCl), boron trichloride (BCl), or the like. ３ The developing gas may contain at least one selected from the group consisting of organic acids (e.g., carboxylic acids, alcohols), and β-dicarbonyl compounds. The carboxylic acid in the developing gas may be, for example, formic acid (HCOOH), acetic acid (CH ３ COOH), trichloroacetic acid (CCl ３ COOH), monofluoroacetic acid (CFH ２ COOH), difluoroacetic acid (CF ２ FCOOH), trifluoroacetic acid (CF ３ COOH) chloro-difluoroacetic acid (CClF ２ COOH), sulfur-containing acetic acid, thioacetic acid (CH ３ COSH), thioglycolic acid (HSCH ２ COOH), trifluoroacetic anhydride ((CF ３ CO) ２ O), and acetic anhydride ((CH ３ CO) ２ O) may contain at least one selected from the group consisting of

[0059] (Step ST20: Supplying Etching Gas to Etch the Base Film) Subsequently, in step ST20, as shown in FIG. 11, an etching gas is supplied into the processing chamber 102 to etch the base film UF. FIG. 11 is a cross-sectional view showing an example of the first substrate W1 after step ST20. In step ST20, the first region MF1 on the base film UF may be considered as a metal-containing mask. In this case, the base film UF may be etched using the metal-containing mask.

[0060] In step ST20, plasma may not be generated from the etching gas, and in this case, step ST20 may be performed by chemical dry etching without using plasma.

[0061] (Step ST21: Transporting the First Substrate W1 Out of the Processing Chamber 102) Subsequently, in step ST21, the first substrate W1 is transported out of the processing chamber 102. For example, the first substrate W1 may be transported out of the processing chamber 102 by a transport device.

[0062] The above-described steps ST13, ST19, and ST20 may be performed in situ in the same processing chamber 102 in the heat treatment apparatus 100, for example. Alternatively, steps ST13, ST19, and ST20 may be performed in different chambers. For example, after step ST19, the first substrate W1 may be unloaded from the processing chamber 102 and then loaded into a processing chamber in the plasma processing apparatus. This processing chamber may be the plasma processing chamber 10 in the plasma processing apparatus 1. When step ST20 is performed in the plasma processing chamber 10, plasma may be generated from an etching gas. Step ST20 may be performed by reactive ion etching using plasma.

[0063] (Process ST22: Providing Second Substrate W2 to Processing Chamber 102) Subsequently, in process ST22, the second substrate W2 is provided into the processing chamber 102. The second substrate W2 may be a dummy wafer. At the start of process ST22, a metal-containing material MS2 has been formed on the surface of the processing chamber 102 or at least one of the components disposed in the processing chamber 102 by at least one substrate processing step among process ST13, process ST16, process ST19, or process ST20, as shown in FIG. 12. FIG. 12 is a partially enlarged cross-sectional view showing an example of the processing chamber 102 when the second substrate W2 is provided into the processing chamber 102. In the example of FIG. 12, the metal-containing material MS2 is formed on the pre-coat film MS1 formed in process ST11. The metal-containing material MS2 may be a particle, a film, or a layer.

[0064] The metal-containing material MS2 may contain the same metal as the metal-containing film MK and the metal-containing resist MF. The metal-containing material MS2 may contain, for example, tin (Sn). The metal-containing material MS2 may contain, for example, tin oxide.

[0065] (Process ST23: Supplying a first process gas G1 to replace the metal contained in the metal-containing material MS2 with silicon) Subsequently, in process ST23, as shown in FIG. 13, a first process gas is supplied into the process chamber 102 to expose the metal-containing material MS2 to the first process gas G1. This replaces the metal contained in the metal-containing material MS2 with silicon. FIG. 13 is a partially enlarged cross-sectional view showing an example of the process chamber 102 when process ST23 is performed.

[0066] In the example of FIG. 13 , the metal contained in the metal-containing material MS2 is substituted with silicon, and a silicon-containing material MS3 is formed from the metal-containing material MS2. As a result, a silicon-containing material MS3 is formed on the pre-coat film MS1. In step ST23, a silicon-containing gas is reacted with the metal-containing material MS2 to substitute a metal element (e.g., tin element) contained in the metal-containing material MS2 with silicon element. When the metal-containing material MS2 contains a metal oxide (e.g., tin oxide), the metal-containing material MS2 contains a bond between tin and oxygen (Sn—O bond). In this case, in step ST23, the Sn—O bond in the metal-containing material MS2 may be replaced with a bond between silicon and oxygen (Si—O bond). As a result, a silicon-containing material MS3 may be formed from the metal-containing material MS2. In one exemplary embodiment, in step ST23, plasma may not be generated from the first process gas G1. The metal present in the metal-containing material MS2 may be substituted with tin without generating plasma. Alternatively, in step ST23, plasma may be generated from the first processing gas G1 using the plasma processing apparatus 1 shown in FIG. 2 or 3.

[0067] An example of the silicon-containing gas contained in the first process gas G1 in process ST23 may be the same as the example of the silicon-containing gas that may be contained in the pre-coat gas GP in process ST11. The silicon-containing gas contained in the first process gas G1 may be the same as or different from the silicon-containing gas that may be contained in the pre-coat gas GP.

[0068] In step ST23, the pressure in the processing chamber 102 may be controlled. In step ST23, the pressure in the processing chamber 102 may be set within the following ranges: The pressure in the processing chamber 102 may be 13.3 Pa (100 mTorr) or higher; The pressure in the processing chamber 102 may be 133 Pa (1 Torr) or higher; The pressure in the processing chamber 102 may be 665 Pa (5 Torr) or higher; The pressure in the processing chamber 102 may be 13.3 kPa (100 Torr) or lower. The pressure in the processing chamber 102 set in step ST23 may be the same as the pressure set in the previous step (e.g., step ST19 and step ST20) or may be higher than the pressure set in the previous step.

[0069] In process ST23, the substrate support part 121 may be heated. In process ST23, the temperature of the substrate support part 121 may be set within the following ranges. The temperature of the substrate support part 121 may be 30° C. or higher. The temperature of the substrate support part 121 may be 60° C. or higher. The temperature of the substrate support part 121 may be 100° C. or higher. The temperature of the substrate support part 121 may be 200° C. or higher. The temperature of the substrate support part 121 may be 300° C. or lower. The temperature of the substrate support part 121 set in process ST23 may be the same as the temperature set in the previous process (e.g., process ST19 and process ST20), or may be higher than the temperature set in the previous process.

[0070] (Step ST24: Supplying a Second Process Gas G2 to Remove the Silicon-Containing Material MS3) Subsequently, in step ST24, as shown in FIG. 14, a second process gas G2 is supplied into the process chamber 102 to remove the silicon-containing material MS3 formed from the metal-containing material MS2 in step ST23. In other words, step ST24 is a cleaning process within the process chamber 102. FIG. 14 is a partially enlarged cross-sectional view showing an example of the process chamber 102 when step ST24 is performed. In step ST24, a second process gas G2 is supplied into the process chamber 102 to expose the silicon-containing material MS3 to the second process gas G2. This removes the silicon-containing material MS3. The precoat film MS1 may be etched by exposing it to the second process gas G2. The thickness of the precoat film MS1 after etching may be approximately half the thickness of the precoat film MS1 formed in step ST11. Alternatively, the precoat film MS1 may not be etched in step ST24. In this case, the thickness of the precoat film MS1 does not need to change from the thickness at the time of forming it in step ST11.

[0071] In step ST24, plasma may not be generated from the second process gas G2. In this case, step ST24 may be dry cleaning by chemical dry etching without using plasma. The second process gas G2 may contain a fluorine-containing gas. The second process gas G2 may contain a nitrogen-containing gas. Examples of the fluorine-containing gas include hydrogen fluoride gas. Examples of the nitrogen-containing gas include ammonia gas.

[0072] In step ST24, plasma may be generated from the second process gas G2 using the plasma processing apparatus 1 of FIG. 2 or 3. In this case, step ST24 may be dry cleaning by reactive ion etching using plasma. The second process gas G2 may contain at least one gas selected from the group consisting of a fluorine-containing gas and an oxygen-containing gas. The fluorine-containing gas may be CF ４ Fluorocarbon gases such as NF ３The second process gas G2 may contain a fluorine-containing gas. When the precoat film MS1 is a silicon-containing film, the second process gas G2 may contain a fluorine-containing gas. In this case, the silicon-containing material MS3 can be efficiently removed by the fluorine-containing gas, and the silicon-containing film can be etched with a high selectivity. Alternatively, when the precoat film MS1 is a carbon-containing film, the second process gas G2 may contain a fluorine-containing gas and an oxygen-containing gas. In this case, the silicon-containing material MS3 can be efficiently removed by the fluorine-containing gas, and the carbon-containing film can be etched with a high selectivity by the oxygen-containing gas.

[0073] The pressure in the processing chamber 102 in step ST24 may be the same as or higher than the pressure in the processing chamber 102 in step ST23. In step ST24, the substrate support 121 may be heated. The temperature of the substrate support 121 in step ST24 may be the same as or higher than the temperature of the substrate support 121 in step ST23.

[0074] (Process ST25: Supplying a third process gas G3 to coat a silicon-containing film MS10 on the surface of the process chamber 102 or the component) Subsequently, in process ST25, as shown in FIG. 15, a third process gas G3 containing a silicon-containing gas is supplied into the process chamber 102 to coat a silicon-containing film MS10 on at least one surface of the process chamber 102 or the component. FIG. 15 is a partially enlarged cross-sectional view showing an example of the process chamber 102 when process ST25 is performed. The silicon-containing film MS10 formed by the third process gas G3 in process ST25 may be the same film as the pre-coat film MS1 formed by the pre-coat gas GP in process ST11.

[0075] 15 , a third process gas G3 is supplied to coat the pre-coat film MS1 remaining after step ST24 with a silicon-containing film MS10. As a result, the silicon-containing film MS10 coats the inner surface of the process chamber 102, the surface of the ring assembly 125, and the surface of the substrate support 121. The total thickness of the silicon-containing film MS10 and the pre-coat film MS1 may be equal to or greater than the thickness of the pre-coat film MS1 at the time of formation in step ST11.

[0076] The silicon-containing gas contained in the third process gas G3 in step ST25 may be the same as the silicon-containing gas contained in the pre-coat gas GP. The silicon-containing gas contained in the third process gas G3 may be the same as or different from the silicon-containing gas contained in the pre-coat gas GP.

[0077] In one exemplary embodiment, plasma may not be generated from the third process gas G3 in step ST25. The silicon-containing film MS10 may be coated without generating plasma. Alternatively, plasma may be generated from the third process gas G3 in step ST25 using the plasma processing apparatus 1 shown in FIG. 2 or 3 .

[0078] In one exemplary embodiment, in step ST25, the third process gas G3 may contain a carbon-containing gas instead of a silicon-containing gas. In this case, at least one surface of the process chamber 102 or the component is coated with a carbon-containing film instead of the silicon-containing film MS10. The carbon-containing gas contained in the third process gas G3 may be the same as or different from the carbon-containing gas that may be contained in the pre-coat gas GP.

[0079] (Step ST26: Transferring the Second Substrate W2 Out of the Processing Chamber 102) Subsequently, in step ST26, the second substrate W2 is transferred out of the processing chamber 102.

[0080] (Process ST27: Determining Whether or Not to Perform Substrate Processing on a New First Substrate W1) Then, in process ST27, it is determined whether or not to perform substrate processing on a new first substrate W1. By coating at least one surface of the processing chamber 102 or the component with the silicon-containing film MS10 in process ST25, metal is less likely to adhere to the surface of the processing chamber 102 or the component during substrate processing on the new first substrate W1. If substrate processing is to be performed on the new first substrate W1 (process ST27: YES), the new first substrate W1 is provided in the processing chamber 102 (process ST12), and processing from process ST13 onwards is performed. If substrate processing is not to be performed on the new first substrate W1 (process ST27: NO), the method MT1 ends.

[0081] According to the method MT1, the metal contained in the metal-containing material MS2 is replaced with silicon in step ST23, which makes it possible to suppress contamination of the processing chamber 102 or components by the metal contained in the metal-containing material MS2 after step ST23.

[0082] In step ST24, after step ST23, a second process gas G2 may be supplied into the process chamber 102 to remove the silicon-containing material MS3 formed from the metal-containing material MS2 in step ST23. In this case, the silicon-containing material MS3 is removed by a reaction between the second process gas G2 and the silicon-containing material MS3.

[0083] In step ST24, plasma may not be generated from the second process gas G2, which can prevent damage to the process chamber 102 or components caused by plasma.

[0084] Although various exemplary embodiments have been described above, various additions, omissions, substitutions, and modifications may be made without being limited to the above-described exemplary embodiments. In the above-described exemplary embodiment, as shown in FIG. 16 , the method MT1 may further include step ST28, in which step ST23 and step ST24 are repeated before step ST25. In this case, removal of the silicon-containing material MS3 is further promoted. In the method MT1, step ST22 may be omitted. That is, step ST23 and subsequent steps may be performed without a substrate being provided in the processing chamber 102. As an example of a substrate processing method, a series of processes including film formation (step ST13), exposure (step ST16), development (step ST19), and etching (step ST20) has been described. The substrate processing process is not limited to this example and may include at least one of step ST13, step ST16, step ST19, or step ST20, or may include other processing steps. In this case, a metal-containing material MS2 may be formed on at least one surface of the processing chamber 102 or a component disposed in the processing chamber 102.

[0085] In the method MT1, a metal-containing material MS2 may be formed on the first substrate W1 by at least one of the substrate processing steps of step ST13, step ST16, step ST19, or step ST20. In this case, the substrate processing method may include a step of supplying a first processing gas G1 containing a silicon-containing gas into the processing chamber 102 to replace the metal contained in the metal-containing material MS2 adhering to the first substrate W1 with silicon. FIG. 17 is a flowchart of a substrate processing method according to a modified example (hereinafter referred to as "method MT2"). Method MT2 is the same as method MT1 except that it does not include steps ST21, ST22, and ST26. In method MT2, the first substrate W1 does not need to be unloaded from the processing chamber 102 after step ST20 is completed. This allows the steps from step ST23 onwards to be performed with the first substrate W1 disposed in the processing chamber 102.

[0086] The method MT2 is performed with the first substrate W1 disposed in the process chamber 102, and may include a step (step ST23) of substituting silicon for the metal contained in the metal-containing material MS2 adhered to the first substrate W1 in step ST20 or the like. Figure 18 is a diagram schematically illustrating an example of the process chamber when a first process gas G1 is supplied to the process chamber in step ST23 to substitute silicon for the metal contained in the metal-containing material MS2 adhered to the first substrate W1. The heat treatment apparatus 100 may further include a gas nozzle main body 190, a nozzle tip 191, a nozzle movement mechanism 210, and a heat source 180. The gas nozzle main body 190 and the nozzle tip 191 constitute a gas nozzle.

[0087] In the example of FIG. 18 , the gas nozzle body 190 is provided on the sidewall of the processing chamber 102. The position at which the gas nozzle body 190 is provided on the sidewall is not limited to one location, and multiple gas nozzle bodies 190 may be provided at multiple locations on the sidewall. One end of the gas nozzle body 190 is connected to a gas supply unit 170 provided outside the processing chamber 102 via a gas supply pipe 192. The other end of the gas nozzle body 190 is located inside the processing chamber 102 and is connected to a nozzle tip 191. A first processing gas G1 is discharged from the nozzle tip 191. The gas nozzle body 190 and the nozzle tip 191 may be moved to desired positions by a nozzle moving mechanism 210. The nozzle moving mechanism 210 may operate in response to an instruction from the control unit 200. For example, the nozzle moving mechanism 210 may move the gas nozzle main body 190 in the extension direction of the gas nozzle main body 190 or may extend or retract the nozzle tip 191 so that the nozzle tip 191 reaches a desired position in the in-plane direction of the substrate support 121. The nozzle moving mechanism 210 may control the bending angle so that the nozzle tip 191 is bent at a desired angle from an axis A1, which is the extension direction of the gas nozzle main body 190. The bending angle is the angle between the axis A1 and an axis A2, which is the extension direction of the nozzle tip 191. The nozzle moving mechanism 210 may fix the position and bending angle of the nozzle tip 191 described above. When the gas nozzle main body 190 and the nozzle tip 191 are not in use (e.g., during the etching process in process ST20), the nozzle moving mechanism 210 may move the gas nozzle main body 190 and the nozzle tip 191 so that the nozzle tip 191 is hidden by a sidewall of the processing chamber 102.

[0088] The heat source 180 is provided on a sidewall of the processing chamber 102. The heat source 180 may be configured to heat the first substrate W1 located in the processing chamber 102. The heat source 180 may be an infrared source, an electromagnetic wave source, or a laser source. The electromagnetic wave source is, for example, a microwave source or an RF wave source. Heating the first substrate W1 by the heat source 180 may promote the substitution of metal contained in the metal-containing material MS2 attached to the first substrate W1 with silicon.

[0089] The nozzle tip 191 may be configured to inject the first process gas G1 toward at least one portion of the front surface, back surface, or bevel of the first substrate W1. Step ST23 in the method MT2 may be performed while the first substrate W1 is lifted up. The first substrate W1 is lifted up or down, for example, by raising or lowering the lift pins 123. When the first substrate W1 is lifted up, the first process gas G1 is injected, for example, with the nozzle tip 191 facing the back surface or bevel (edge ​​or peripheral portion of the first substrate W1) of the first substrate W1. Thus, in step ST23, metal contained in the metal-containing material MS2 adhering to the back surface or bevel of the first substrate W1 is replaced with silicon. Alternatively, during step ST23, the control unit 200 may control the nozzle moving mechanism 210 to change the bending angle of the nozzle tip 191. This allows the nozzle tip 191 to eject the first process gas G1 onto both the back surface and the bevel of the first substrate W1. In this case, in step ST23, the metal contained in the metal-containing material MS2 adhering to both the back surface and the bevel of the first substrate W1 is replaced with silicon.

[0090] Step ST23 may be performed with the first substrate W1 in a lifted-down state. In this case, for example, the first process gas G1 is discharged with the nozzle tip 191 facing the surface of the first substrate W1. As a result, in step ST23, metal contained in the metal-containing material MS2 adhering to the surface of the first substrate W1 is replaced with silicon. Alternatively, the control unit 200 may control the lift pins 123 to switch between lifting up and lifting down the first substrate W1 during step ST23.

[0091] Step ST23 in the method MT2 may be performed in a chamber other than the processing chamber 102. The heat treatment apparatus 100 may process the first substrate W1 in the processing chamber 102 (first chamber) and transfer the first substrate W1 out of the processing chamber 102 after step ST20. The heat treatment apparatus 100 may then provide the first substrate W1 to a second chamber and supply the first processing gas G1 into the second chamber to replace the metal contained in the metal-containing material MS adhered to the first substrate W1 by the processing in the processing chamber 102 with silicon.

[0092] 19 is a schematic diagram illustrating an example of another chamber used in step ST23 when a first process gas G1 is supplied to replace metal contained in a metal-containing material MS2 attached to a first substrate W1 with silicon. The second chamber 300 includes, for example, a substrate support 301 (second substrate support) similar to the substrate support 121 (first substrate support) in the process chamber 102. The second chamber 300 further includes a gas nozzle body 390, a nozzle tip 391, a nozzle movement mechanism 310, a heat source 380, and an exhaust port 303. The gas nozzle body 390 and the nozzle tip 391 form a gas nozzle. The gas nozzle body 390, the nozzle tip 391, the nozzle movement mechanism 310, and the heat source 380 have the same configurations and operate in the same manner as the gas nozzle body 190, the nozzle tip 191, the nozzle movement mechanism 210, and the heat source 180 in the process chamber 102. The exhaust port 303 is connected to an exhaust mechanism via, for example, an exhaust pipe. In the example of FIG. 19 , the substrate support unit 301 includes, for example, a holder 302 and a rotation drive unit 304. The holder 302 supports the first substrate W1 and holds and fixes the first substrate W1 by, for example, vacuum suction or the like. The diameter of the holder 302 is smaller than the diameter of the first substrate W1. Therefore, the bevel and part of the back surface of the first substrate W1 protrude from the holder 302. The rotation drive unit 304 is, for example, an actuator powered by an electric motor or the like. The rotation drive unit 304 rotates the holder 302 in response to instructions from the control unit 200, thereby rotating the first substrate W1.

[0093] In the second chamber 300, the first process gas G1 may be discharged with the nozzle tip 391 facing the backside or bevel of the first substrate W1. The heat source 380 may be configured to heat the first substrate W1 located in the second chamber 300. The control unit 200 may control the position, bending angle, and rotation angle of the nozzle tip 391 during process ST23. The nozzle moving mechanism 310 may move the gas nozzle body 390 and the nozzle tip 391 when they are not in use so that the nozzle tip 391 is hidden by the sidewall of the second chamber 300. The position at which the gas nozzle body 390 is provided on the sidewall is not limited to one location, and multiple gas nozzle bodies 390 may be arranged at multiple locations on the sidewall.

[0094] Various experiments performed to evaluate Method MT1 are described below, but the experiments described below are not intended to limit the present disclosure.

[0095] (First Experiment) In the first experiment, a substrate was placed on a substrate support in a chamber, the substrate including a film containing tin (Sn).

[0096] Thereafter, dichlorosilane gas was supplied into the chamber without generating plasma. The pressure inside the chamber was 665 Pa (5 Torr). The temperature of the substrate support was 100° C. The processing time was 20 minutes.

[0097] (Second Experiment) An experiment was carried out under the same conditions as the first experiment, except that the temperature of the substrate support was 50°C.

[0098] (Results of the First and Second Experiments) The cross sections of the substrates obtained in the first and second experiments were observed using a high-angle annular dark field scanning transmission microscope (HAADF-STEM). Furthermore, the elements contained in the films were analyzed by energy dispersive X-ray spectroscopy (EDX).

[0099] In the second experiment, the EDX results showed that almost no silicon was detected as an element contained in the film, but only tin was detected. On the other hand, in the first experiment, the EDX results showed that almost no tin was detected as an element contained in the film, but only silicon and oxygen were detected. From these results, the substitution of tin with silicon was confirmed in the first experiment. In addition, the amount of oxygen detected in the first experiment was visually less than the amount of oxygen detected in the second experiment.

[0100] Various exemplary embodiments included in the present disclosure are now described in [E1] to [E23] below.

[0101] [E1] A substrate processing method comprising: (a) a step of processing a substrate in a chamber, whereby a metal-containing material is formed on at least one surface of the chamber, the substrate, or a component disposed in the chamber by processing the substrate; and (b) after (a), a step of supplying a first process gas containing a silicon-containing gas into the chamber to replace the metal contained in the metal-containing material with silicon. [E2] The substrate processing method of [E1], in which (b) plasma is not generated from the first process gas. [E3] The substrate processing method of [E1], further comprising: (c) after (b), supplying a second process gas into the chamber to remove the silicon-containing material formed from the metal-containing material in (b). [E4] The substrate processing method of [E3], in which (c) plasma is not generated from the second process gas. [E5] The substrate processing method of [E3], in which plasma is generated from the second process gas in (c). [E6] The substrate processing method according to any one of [E3] to [E5], further comprising the step of repeating steps (b) and (c). [E7] The substrate processing method according to any one of [E1] to [E6], wherein step (b) is performed while the substrate is placed in the chamber, and comprises substituting, with silicon, the metal contained in the metal-containing material adhered to the substrate by step (a). [E8] The substrate processing method according to [E7], wherein step (b) is performed while the substrate is lifted up, and substituting, with silicon, the metal contained in the metal-containing material adhered to at least one of the backside or bevel of the substrate. [E9] The substrate processing method according to any one of [E3] to [E5], further comprising the step of (d) after step (c), supplying a third process gas containing a silicon-containing gas into the chamber, thereby coating at least one surface of the chamber or the component with a silicon-containing film. [E10] The substrate processing method according to [E9], wherein, in step (d), plasma is not generated from the third process gas. [E11] The substrate processing method according to any one of [E1] to [E10], wherein the metal-containing substance contains tin as the metal.[E12] The substrate processing method according to any one of [E1] to [E11], wherein the silicon-containing gas includes at least one selected from the group consisting of a gas containing silicon and chlorine, a gas containing silicon and bromine, a gas containing silicon and iodine, a gas containing silicon and hydrogen, and an aminosilane gas. [E13] The substrate processing method according to [E12], wherein the silicon-containing gas includes dichlorosilane. [E14] The substrate processing method according to any one of [E1] to [E13], wherein in (b), the pressure in the chamber is 13.3 Pa or higher. [E15] The substrate processing method according to any one of [E1] to [E14], wherein in (b), the temperature of the chamber or the component is 60° C. or higher. [E16] The substrate processing method according to any one of [E1] to [E15], wherein in (a), the substrate comprises an undercoat film and a metal-containing resist on the undercoat film, the metal-containing resist having a first exposed region and a second unexposed region, and (a) comprises: (a1) supplying a developing gas to remove the second region. [E17] The substrate processing method according to any one of [E1] to [E16], wherein in (a), the substrate comprises an undercoat film and a metal-containing mask on the undercoat film, and (a) comprises: (a2) supplying an etching gas into the chamber to etch the undercoat film using the metal-containing mask. [E18] The substrate processing method according to any one of [E1] to [E17], wherein in (a), the substrate comprises an undercoat film, and (a) comprises: (a3) ​​forming a metal-containing film on the undercoat film. [E19] A substrate processing method comprising: (a) processing a substrate in a chamber, wherein processing the substrate results in the formation of a metal-containing material on at least one surface of the chamber or a component disposed in the chamber; and (b) after (a), supplying a first process gas containing a silicon-containing gas into the chamber and exposing the metal-containing material to the first process gas.[E20] A substrate processing method comprising: (a) processing a substrate in a chamber; and (b) supplying a first process gas containing a silicon-containing gas into the chamber to replace metal contained in the metal-containing material adhered to the substrate by (a) with silicon. [E21] A substrate processing apparatus comprising: a chamber; a substrate support for supporting a substrate in the chamber; a gas supply unit for supplying a first process gas containing a silicon-containing gas into the chamber; and a controller, wherein the controller is configured to control the substrate processing apparatus to process the substrate in the chamber and to form a metal-containing material on a surface of at least one of the chamber, the substrate, or a component disposed in the chamber by processing the substrate, and the controller is configured to control the gas supply unit to supply the first process gas into the chamber after processing the substrate to replace metal contained in the metal-containing material with silicon. [E22] The substrate processing apparatus according to [E21], further comprising a gas nozzle for discharging the first process gas onto at least one portion of a front surface, a back surface, or a bevel of the substrate. [E23] A substrate processing apparatus comprising: a first chamber; a second chamber; a first substrate support part for supporting a substrate in the first chamber; a second substrate support part for supporting the substrate in the second chamber; a gas supply part for supplying a first process gas containing a silicon-containing gas into the second chamber; and a control part, wherein the control part is configured to process the substrate in the first chamber, and to control the gas supply part to supply the first process gas into the second chamber and replace metal contained in a metal-containing material adhered to the substrate by processing in the first chamber with silicon.

[0102] 1...plasma processing apparatus (substrate processing apparatus), 100...heat processing apparatus (substrate processing apparatus), 10...plasma processing chamber (chamber), 102...processing chamber (chamber, first chamber), 11, 121...substrate support part (first substrate support part), 2, 200...control part, 20, 170...gas supply part, 300...second chamber, 301...substrate support part (second substrate support part), G1...first processing gas, MS2...metal-containing substance, MT1...method (substrate processing method), W...substrate.

Claims

1. A substrate processing method comprising: (a) processing a substrate in a chamber, wherein processing the substrate results in the formation of a metal-containing material on at least one surface of the chamber, the substrate, or a component disposed within the chamber; and (b) after (a), supplying a first process gas containing a silicon-containing gas into the chamber to replace metal contained in the metal-containing material with silicon.

2. The substrate processing method according to claim 1, wherein in (b), no plasma is generated from the first processing gas.

3. The substrate processing method of claim 1, further comprising the step of: (c) after (b), supplying a second processing gas into the chamber to remove the silicon-containing material formed from the metal-containing material in (b).

4. The substrate processing method according to claim 3, wherein in (c), no plasma is generated from the second processing gas.

5. The substrate processing method according to claim 3, wherein in step (c), a plasma is generated from the second processing gas.

6. The substrate processing method according to any one of claims 3 to 5, further comprising the step of repeating steps (b) and (c).

7. A substrate processing method according to any one of claims 1 to 5, wherein (b) is performed while the substrate is placed in the chamber, and includes substituting metal contained in the metal-containing material adhered to the substrate by (a) with silicon.

8. The substrate processing method according to claim 7, wherein (b) is performed in a state where the substrate is lifted up, and metal contained in the metal-containing material attached to at least one of the back surface or bevel of the substrate is replaced with silicon.

9. The substrate processing method according to any one of claims 3 to 5, further comprising the step of: (d) after (c), supplying a third process gas containing a silicon-containing gas into the chamber to coat at least one surface of the chamber or the component with a silicon-containing film.

10. The substrate processing method according to claim 9, wherein in (d), no plasma is generated from the third processing gas.

11. The substrate processing method according to any one of claims 1 to 5, wherein the metal-containing substance contains tin as the metal.

12. The substrate processing method according to any one of claims 1 to 5, wherein the silicon-containing gas includes at least one selected from the group consisting of a gas containing silicon and chlorine, a gas containing silicon and bromine, a gas containing silicon and iodine, a gas containing silicon and hydrogen, and an aminosilane gas.

13. The substrate processing method of claim 12, wherein the silicon-containing gas comprises dichlorosilane.

14. The substrate processing method according to any one of claims 1 to 5, wherein in (b), the pressure inside the chamber is 13.3 Pa or more.

15. A substrate processing method according to any one of claims 1 to 5, wherein in (b), the temperature of the chamber or the part is 60°C or higher.

16. A substrate processing method according to any one of claims 1 to 5, wherein in (a), the substrate comprises an undercoat film and a metal-containing resist on the undercoat film, the metal-containing resist having an exposed first region and an unexposed second region, and (a) includes the step of: (a1) supplying a developing gas to remove the second region.

17. A substrate processing method according to any one of claims 1 to 5, wherein in (a), the substrate comprises an underlayer film and a metal-containing mask on the underlayer film, and (a) includes the step of: (a2) supplying an etching gas into the chamber and etching the underlayer film using the metal-containing mask.

18. A substrate processing method according to any one of claims 1 to 5, wherein in (a), the substrate comprises an undercoat film, and (a) includes the step of (a3) ​​forming a metal-containing film on the undercoat film.

19. A substrate processing method comprising: (a) processing a substrate in a chamber, wherein processing the substrate forms a metal-containing material on at least one surface of the chamber or a component disposed in the chamber; and (b) after (a), supplying a first process gas including a silicon-containing gas into the chamber and exposing the metal-containing material to the first process gas.

20. A substrate processing method comprising: (a) processing a substrate in a chamber; and (b) supplying a first processing gas containing a silicon-containing gas into the chamber to replace metal contained in the metal-containing material adhered to the substrate by (a) with silicon.

21. A substrate processing apparatus comprising: a chamber; a substrate support unit for supporting a substrate in the chamber; a gas supply unit for supplying a first process gas containing a silicon-containing gas into the chamber; and a control unit, wherein the control unit is configured to control the substrate processing apparatus so that the substrate is processed in the chamber and a metal-containing substance is formed on a surface of at least one of the chamber, the substrate, or a component disposed in the chamber by processing the substrate; and the control unit is configured to control the gas supply unit so that after the substrate is processed, the first process gas is supplied into the chamber to replace the metal contained in the metal-containing substance with silicon.

22. The substrate processing apparatus of claim 21, further comprising a gas nozzle that discharges the first process gas onto at least one portion of the front surface, back surface, or bevel of the substrate.

23. A substrate processing apparatus comprising: a first chamber; a second chamber; a first substrate support for supporting a substrate in the first chamber; a second substrate support for supporting the substrate in the second chamber; a gas supply unit for supplying a first process gas containing a silicon-containing gas into the second chamber; and a control unit, wherein the control unit is configured to process the substrate in the first chamber and control the gas supply unit to supply the first process gas into the second chamber and replace metal contained in a metal-containing material adhered to the substrate by processing in the first chamber with silicon.

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