Processing method and substrate processing device

Abstract

Provided are a processing method and a substrate processing device that shorten the time until a processing chamber is opened.　According to the present invention, a processing method that involves opening a processing chamber of a substrate processing device that performs processing on a substrate using a processing gas that contains fluorine includes a step for supplying a gas that contains hydrogen and oxygen into the processing chamber, a step for discharging the gas inside the processing chamber after the gas that contains hydrogen and oxygen has been supplied into the processing chamber, a step for repeating the step for supplying the gas that contains hydrogen and oxygen and the step for discharging the gas inside the processing chamber, and, after the repetition step, a step for bringing the inside of the processing chamber to atmospheric pressure.

Description

Processing method and substrate processing apparatus

[0001] The present disclosure relates to a processing method and a substrate processing apparatus.

[0002] Patent Document 1 describes an etching method for etching a substrate using plasma of a processing gas containing fluorine.

[0003] Japanese Patent Application Laid-Open No. 2019-121685

[0004] In one aspect, the present disclosure provides a processing method and a substrate processing apparatus that reduces the time required to open a processing chamber.

[0005] In order to solve the above problem, according to one aspect, there is provided a processing method for opening a processing chamber of a substrate processing apparatus that processes a substrate using a processing gas containing fluorine, the processing method comprising the steps of: supplying a gas containing hydrogen and oxygen into the processing chamber; evacuating the gas in the processing chamber after supplying the gas containing hydrogen and oxygen; repeating the steps of supplying the gas containing hydrogen and oxygen and evacuating the gas in the processing chamber; and, after the repeating step, bringing the pressure in the processing chamber to atmospheric pressure.

[0006] According to one aspect, it is possible to provide a processing method and a substrate processing apparatus that shorten the time required to open a processing chamber.

[0007] 1 is a diagram illustrating an example of the configuration of a capacitively coupled plasma processing apparatus according to a first embodiment; FIG. 2 is a flowchart illustrating an example of a first processing method for opening a plasma processing chamber; FIG. 3 is a flowchart illustrating an example of a second processing method for opening a plasma processing chamber; FIG. 4 is a cross-sectional view illustrating a process for removing fluorine in the first processing method; FIG. 5 is a cross-sectional view illustrating a process for removing fluorine in the first processing method; FIG. 6 is a cross-sectional view illustrating a process for removing fluorine in the first processing method; FIG. 7 is a cross-sectional view illustrating a process for removing fluorine in the second processing method; FIG. 8 is a cross-sectional view illustrating a process for removing fluorine in the second processing method; FIG. 9 is a cross-sectional view illustrating a process for removing fluorine in the second processing method; FIG. 10 is a cross-sectional view illustrating a process for removing fluorine in the second processing method; FIG. 11 is a horizontal cross-sectional view illustrating an example of the arrangement of gas nozzles;

[0008] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and redundant explanations may be omitted.

[0009] [Plasma Processing System] An example of the configuration of a plasma processing system will be described below. Fig. 1 is an example of a diagram for explaining an example of the configuration of a capacitively coupled plasma processing apparatus (substrate processing apparatus) 1.

[0010] The plasma processing system includes a capacitively coupled plasma processing apparatus 1 and a controller 2. The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power supply system 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 has at least one gas inlet for supplying at least one processing gas into the plasma processing space 10s and at least one gas outlet for exhausting gas from the plasma processing space 10s. 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.

[0011] 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.

[0012] 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 chuck electrode 1111b disposed within the ceramic member 1111a. The electrostatic chuck electrode 1111b is also referred to as a clamping electrode. In one embodiment, the electrostatic chuck electrode 1111b is electrically connected or coupled to a chuck power supply. The chuck power supply may be a DC power supply or an AC power supply. 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 be formed on 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. At least one bias electrode electrically connected to or coupled to a power supply 31 and / or a power supply 32 (described later) may be disposed within the ceramic member 1111a. In this case, the at least one bias electrode functions as a lower electrode. Alternatively, the conductive member of the base 1110 and the bias electrode within the ceramic member 1111a may function as multiple lower electrodes. In one embodiment, the first voltage generation unit 32a, which functions as a voltage pulse generation unit (described later), is electrically connected to or coupled to the bias electrode within the ceramic member 1111a, and the first RF generation unit 31a (described later) is electrically connected to or coupled to the conductive member of the base 1110. The electrostatic chuck electrode 1111b may function as a lower electrode. The substrate support 11 therefore comprises at least one bottom electrode.

[0013] 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.

[0014] 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 W 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 back surface of the substrate W and the central region 111a.

[0015] 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.

[0016] 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 one or more flow modulation devices to modulate or pulse the flow rate of the at least one process gas.

[0017] The power supply system 30 includes a power supply 31 electrically connected or coupled to the plasma processing chamber 10. In one embodiment, the power supply 31 is electrically connected or coupled to the plasma processing chamber 10 via at least one impedance matcher. The impedance matcher may be a mechanically controlled matcher or an electronically controlled matcher. The power supply 31 is configured to supply at least one radio frequency (RF) signal (RF power) to at least one lower electrode and / or at least one upper electrode. This generates plasma from at least one process gas supplied to the plasma processing space 10s. Therefore, the power supply 31 can function as at least a part of a plasma generating unit configured to generate plasma from one or more process gases in the plasma processing chamber 10. 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.

[0018] The power supply 31 includes a first RF generator 31a and a second RF generator 31b. The first RF generator 31a is electrically connected or coupled to at least one lower electrode and / or at least one upper electrode and is configured to generate a source RF signal (source RF power) to generate plasma in the plasma processing space 10s. In one embodiment, the first RF generator 31a is electrically connected or coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matcher. 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 generator 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.

[0019] The second RF generator 31b is electrically connected or coupled to at least one lower electrode and configured to generate a bias RF signal (bias RF power). In one embodiment, the second RF generator 31b is electrically connected or coupled to at least one lower electrode via at least one impedance matcher. When the first RF generator 31a is electrically connected or coupled to a lower electrode, the second RF generator 31b may be electrically connected or coupled to the same lower electrode or to another lower electrode. 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.

[0020] The power supply system 30 may also include a power supply 32 electrically connected or coupled to the plasma processing chamber 10. The power supply 32 includes a first voltage generator 32a and a second voltage generator 32b. In one embodiment, the first voltage generator 32a is electrically connected or coupled to at least one lower electrode and configured to generate a first voltage signal. The generated first voltage signal is applied to the at least one lower electrode. In one embodiment, the second voltage generator 32b is electrically connected or coupled to at least one upper electrode and configured to generate a second voltage signal. The generated second voltage signal is applied to the at least one upper electrode.

[0021] In various embodiments, the first and / or second voltage signals may be pulsed. In this case, the first voltage generator 32a and / or the second voltage generator 32b function as a voltage pulse generator configured to generate a sequence of voltage pulses. Thus, the sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. In one embodiment, the sequence of voltage pulses includes multiple cycles, each cycle including a burst of voltage pulses during a first period and a constant reference voltage during a second period. That is, the bursts of voltage pulses are repeated in the sequence of voltage pulses. The absolute value of the voltage level of the voltage pulses is greater than the absolute value of the voltage level of the reference voltage. The voltage pulses may have an arbitrary waveform, such as a rectangular, trapezoidal, triangular, or combination thereof, and the arbitrary waveform may vary over time. The voltage pulses may have either positive or negative polarity. Furthermore, the sequence of voltage pulses may include one or more positive polarity voltage pulses and one or more negative polarity voltage pulses within one cycle. The first and second voltage generating units 32a and 32b may be provided in addition to the power supply 31, or the first voltage generating unit 32a may be provided instead of the second RF generating unit 31b.

[0022] 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.

[0023] 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 memory unit 2a2, and a communication interface 2a3. The functions performed by the processing unit 2a1 described in this disclosure may be implemented in circuitry or processing circuitry, including general-purpose processors, application-specific processors, integrated circuits, ASICs (Application Specific Integrated Circuits), CPUs (Central Processing Units), conventional circuitry, and / or combinations thereof, programmed to perform the described functions. A processor is considered to be a circuit or processing circuit including transistors and other circuitry. The processor may also be a programmed processor that executes a program stored in the memory unit 2a2. This program may be stored in the memory unit 2a2 in advance or may be acquired via a medium when needed. The acquired program is stored in the storage unit 2a2 and read from the storage unit 2a2 by the processing unit 2a1 for execution. The medium may be various storage media readable by the computer 2a or a communication line connected to the communication interface 2a3. The storage unit 2a2 may include a random access memory (RAM), a read-only memory (ROM), a hard disk drive (HDD), a solid state drive (SSD), or a combination thereof. The communication interface 2a3 may communicate with the plasma processing apparatus 1 via a communication line such as a local area network (LAN).In this disclosure, a circuit, unit, or means is hardware that is programmed to implement or configured to implement a described function. The hardware may be any hardware described in this disclosure or any hardware that is programmed to implement or known to implement the described function. If the hardware is a processor, which is considered a type of circuit, the circuit, means, or unit is a combination of hardware and software used to configure the hardware and / or processor.

[0024] Next, a processing method when the plasma processing chamber 10 of the plasma processing apparatus 1 is opened will be described with reference to FIG.

[0025] FIG. 2 is a flow chart illustrating an example of a first processing method for opening the plasma processing chamber 10 .

[0026] In step S101, the substrate W is subjected to substrate processing. Here, the substrate W is transported into the plasma processing chamber 10, and the substrate W is supported by the substrate support part 11. Next, the control part 2 controls the gas supply part 20 to supply a processing gas into the plasma processing space 10s, thereby performing a desired processing on the substrate W. The control part 2 may also control the power supply 30 to supply a source RF signal (source RF power) for plasma generation to the lower electrode and / or upper electrode, thereby generating plasma of the processing gas, and performing a desired processing on the substrate W with the plasma of the processing gas. Then, when the substrate processing is completed, the processed substrate W is unloaded from the plasma processing chamber 10.

[0027] Here, in the substrate processing in step S101, a desired process (e.g., etching process, film formation process, etc.) is performed on the substrate W using a process gas containing fluorine (F). During this substrate processing, a reaction layer 210 containing fluorine (F) (see FIG. 4A , etc., described later) is formed on the surface of the member 200 in the plasma processing chamber 10. Alternatively, a reaction by-product containing fluorine (F) is deposited on the surface of the member 200 in the plasma processing chamber 10.

[0028] In step S102, it is determined whether or not to open the plasma processing chamber 10. For example, if the plasma processing chamber 10 is to be opened for maintenance or the like (YES in S102), the control unit 2 proceeds to step S103. If the plasma processing chamber 10 is not to be opened (NO in S102), the control unit 2 repeats steps S101 and S102 until the timing to open the plasma processing chamber 10 arrives.

[0029] In step S103, pre-processing is performed. Here, the processing gas containing fluorine (F) remaining in the plasma processing chamber 10 is exhausted. For example, the control unit 2 controls the gas supply unit 20 to supply dry air or N 2 as a purge gas into the plasma processing chamber 10. ２ The process of introducing the gas and the process of exhausting the purge gas by controlling the exhaust system 40 are repeated a predetermined number of times to exhaust the processing gas containing fluorine (F) remaining in the plasma processing chamber 10.

[0030] In step S104, a gas containing hydrogen (H) and oxygen (O) is introduced into the plasma processing chamber 10. Here, the control unit 2 closes a pressure control valve (e.g., an APC (Automatic Pressure Control) valve) of the exhaust system 40 and controls the gas supply unit 20 to introduce the gas containing hydrogen (H) and oxygen (O) into the plasma processing chamber 10.

[0031] Here, the gas containing hydrogen (H) and oxygen (O) is water (H ２ A gas containing hydrogen (H) and oxygen (O) (for example, atmospheric gas) can be used. In addition, a gas containing hydrogen (H) and oxygen (O) can be used, for example, hydrogen peroxide (H ２ O ２ It should be noted that the gas containing hydrogen (H) and oxygen (O) is not limited to these, and gases containing polarizable alcohols such as ethanol, methanol, and propanol may also be used.

[0032] In step S105, the pressure inside the plasma processing chamber 10 is maintained. Here, the control unit 2 controls the gas supply unit 20 and the exhaust system 40 to maintain the pressure inside the plasma processing chamber 10 at a pressure of 10 Torr or higher for a maintenance time of 1 to 10 minutes. This causes the fluorine (F) contained in the reaction layer 210 to react (reduce) with the gas containing hydrogen (H) and oxygen (O). In addition, the fluorine (F) is desorbed from the reaction layer 210, generating a gas containing fluorine (F) (e.g., HF gas).

[0033] In step S106, evacuation is performed. Here, the controller 2 controls the gas supply unit 20 to stop the supply of gas containing hydrogen (H) and oxygen (O), opens the pressure control valve of the exhaust system 40, and depressurizes the inside of the plasma processing chamber 10 to a high vacuum using a vacuum pump (e.g., a turbomolecular pump (TMP)). This exhausts the gas inside the plasma processing chamber 10. As a result, a gas containing fluorine (F) (e.g., HF gas) is exhausted from the plasma processing chamber 10 via the exhaust system 40.

[0034] In step S107, it is determined whether the processes of steps S104, S105, and S106 have been repeated a predetermined number of times. If the processes have not been repeated the predetermined number of times (S107: NO), the control unit 2 returns to step S104 and repeats the processes of steps S104, S105, and S106. If the processes have been repeated the predetermined number of times (S107: YES), the control unit 2 proceeds to step S108.

[0035] In step S108, the plasma processing chamber 10 is opened. Here, dry air, N ２ A moisture-free gas, such as a gas, is introduced into the plasma processing chamber 10 to bring the pressure inside the plasma processing chamber 10 to atmospheric pressure. Then, an operator removes the ceiling (such as the shower head 13) of the plasma processing chamber 10 to open the plasma processing chamber 10.

[0036] FIG. 3 is a flow chart illustrating an example of a second processing method for opening the plasma processing chamber 10 .

[0037] 2, as shown in step S105, fluorine (F) contained in the reaction layer 210 is reacted (reduced) with a gas containing hydrogen (H) and oxygen (O). In contrast, as shown in step S105A, in the treatment method shown in Fig. 3, fluorine (F) contained in the reaction layer 210 is reacted (reduced) with plasma of a gas containing hydrogen (H) and oxygen (O).

[0038] In step S101, substrate processing is performed on the substrate W. In step S102, it is determined whether or not to open the plasma processing chamber 10. If the plasma processing chamber 10 is to be opened (YES in S102), the control unit 2 proceeds to step S103. If the plasma processing chamber 10 is not to be opened (NO in S102), the control unit 2 repeats steps S101 and S102 until the timing to open the plasma processing chamber 10 arrives. In step S103, pre-processing is performed. Note that the processing in steps S101 to S103 is the same as the processing method shown in FIG. 2, and therefore, redundant explanations will be omitted.

[0039] In step S104, a gas containing hydrogen (H) and oxygen (O) is introduced into the plasma processing chamber 10. Here, the control unit 2 closes a pressure control valve (e.g., an APC (Automatic Pressure Control) valve) of the exhaust system 40 and controls the gas supply unit 20 to introduce the gas containing hydrogen (H) and oxygen (O) into the plasma processing chamber 10.

[0040] Here, the gas containing hydrogen (H) and oxygen (O) is water (H ２ A gas containing hydrogen (H) and oxygen (O) (for example, atmospheric gas) can be used. In addition, a gas containing hydrogen (H) and oxygen (O) can be used, for example, hydrogen peroxide (H ２ O ２ Gases containing hydrogen (H) and oxygen (O) may also be used. The gas containing hydrogen (H) and oxygen (O) is not limited to these, and gases containing polarizable alcohols, such as ethanol, methanol, and propanol, may also be used. ２ Gas and O ２ A mixture of gases can also be used. Also, a mixture of fluorine (F)-free hydrocarbon (CxHy) gas and O２ A mixture of gases may also be used.

[0041] In step S105A, plasma of a gas containing hydrogen (H) and oxygen (O) is generated. Here, the control unit 2 controls the power supply 30 (first RF generation unit 31a) to supply a source RF signal (source RF power) for plasma generation to the lower electrode and / or upper electrode, thereby generating plasma of the gas containing hydrogen (H) and oxygen (O). This causes a reaction (reduction reaction) between fluorine (F) contained in the reaction layer 210 and activated species (hydrogen ions, hydrogen radicals, etc.) generated by the plasma. In addition, fluorine (F) is desorbed from the reaction layer 210, generating a gas containing fluorine (F) (e.g., HF gas).

[0042] In step S106, evacuation is performed. In step S107, it is determined whether the processes of steps S104, S105, and S106 have been repeated a predetermined number of times. If the processes have not been repeated the predetermined number of times (S107: NO), the control unit 2 returns to step S104 and repeats the processes of steps S104, S105, and S106. If the processes have been repeated the predetermined number of times (S107: YES), the control unit 2 proceeds to step S108. In step S108, the plasma processing chamber 10 is opened. Note that the processes of steps S106 to S108 are the same as those in the processing method shown in FIG. 2, and therefore, redundant explanations will be omitted.

[0043] Next, the process of removing fluorine (F) in the first processing method shown in Fig. 2 will be described with reference to Figs. 4A to 4C. Figs. 4A to 4C are schematic diagrams illustrating the process of removing fluorine (F) in the first processing method.

[0044] 4A is a schematic diagram showing the state of the surface of the member 200 in the plasma processing chamber 10 in steps S101 to S103. The member 200 is made of silicon (Si), quartz (Qz), or the like. A thermally sprayed film of yttrium (Y) or the like is formed on the surface of the member 200. A reaction layer 210 is formed on the surface of the member 200 by the substrate processing in step S101. The reaction layer 210 is an oxide layer and a fluoride layer, and contains oxygen (O) and fluorine (F). After step S103, the plasma processing space 10s is in a vacuum atmosphere.

[0045] 4B is a schematic diagram showing the state of the surface of the member 200 in the plasma processing chamber 10 in steps S104 and S105. Here, a gas 220 containing hydrogen (H) and oxygen (O) is supplied to the plasma processing space 10s, and reacts with fluorine (F) in the reaction layer 210, resulting in hydrogen (H) termination and the generation of HF gas 251.

[0046] 4C is a schematic diagram showing the state of the surface of the member 200 in the plasma processing chamber 10 after the processes of steps S104 to S106 have been repeated (step S107: YES). In step S106, HF gas 251 is exhausted by drawing a vacuum. Fluorine (F) is also removed from the reaction layer 210, resulting in a hydrogen termination 211.

[0047] Next, the process for removing fluorine (F) in the second processing method shown in Fig. 3 will be described with reference to Figs. 5A to 5C. Figs. 5A to 5C are schematic diagrams illustrating the process for removing fluorine (F) in the second processing method.

[0048] 5A is a schematic diagram showing the state of the surface of the member 200 in the plasma processing chamber 10 in steps S101 to S103. The member 200 is made of silicon (Si), quartz (Qz), or the like. A thermally sprayed film of yttrium (Y) or the like is formed on the surface of the member 200. A reaction layer 210 is formed on the surface of the member 200 by the substrate processing in step S101. The reaction layer 210 is an oxide layer and a fluoride layer, and contains oxygen (O) and fluorine (F). After step S103, the plasma processing space 10s is in a vacuum atmosphere.

[0049] 5B is a schematic diagram showing the state of the surface of the member 200 in the plasma processing chamber 10 in steps S104 to S105A. Here, plasma 230 of a gas containing hydrogen (H) and oxygen (O) is generated in the plasma processing space 10s. Active species 231 (hydrogen ions, hydrogen radicals, etc.) generated by the plasma 230 react with fluorine (F) in the reaction layer 210, resulting in hydrogen (H) termination and the generation of HF gas 251.

[0050] 5C is a schematic diagram showing the state of the surface of the member 200 in the plasma processing chamber 10 after the processes of steps S104 to S106 have been repeated (YES in step S107). In step S106, HF gas 251 is exhausted by evacuation. Fluorine (F) is also removed from the reaction layer 210, resulting in a hydrogen termination 211.

[0051] Next, the process of removing fluorine (F) shown in FIG. 4B in the first processing method shown in FIG. 2 will be further described with reference to FIGS. 6A to 6C. FIGS. 6A to 6C are schematic diagrams illustrating the process of removing fluorine (F) in the first processing method. Here, H is used as the gas 220 containing hydrogen (H) and oxygen (O). ２ An example in which O (for example, moisture contained in atmospheric gas) is used will be described.

[0052] As shown in FIG. 6A, the surface of the member 200 has a metal element (M) and fluorine (F). The metal element (M) is described as, for example, the metal of the member 200 (e.g., Al, etc.), but is not limited to this and may be yttrium (Y) or silicon (Si) of a thermally sprayed film. The metal element (M) is polarized to δ+, and fluorine (F) is polarized to δ-. In addition, H ２ O(l) undergoes self-dissociation as shown in the following reaction formula (1). Therefore, fluorine (F), which is polarized to δ- due to its electronegativity, reacts with H, which is polarized to δ+. ３ O ＋ is attracted (see reference numeral 311).

[0053] 2H ２ O → H ３ O ＋ +OH － ...(1)

[0054] As shown in FIG. 6B, a metal element (M) polarized to δ+ due to electronegativity has OH atoms polarized to δ-. － is attracted (see reference numeral 312). Then, the bond between the metal element (M) and fluorine (F) is broken (see reference numeral 313), and the metal element (M) is converted to OH. － (See reference numeral 314.) Fluorine (F) reacts with H ３ O ＋ and reacts.

[0055] As a result, a bond (M-OH) between the metal element (M) and OH is formed as shown in Fig. 6C, and HF gas is also generated.

[0056] Next, the process of removing fluorine (F) shown in FIG. 5B in the second processing method shown in FIG. 3 will be further described with reference to FIGS. 7A to 7C. FIGS. 7A to 7C are schematic diagrams illustrating the process of removing fluorine (F) in the second processing method. Here, H is used as the gas 220 containing hydrogen (H) and oxygen (O). ２ An example in which O (for example, moisture contained in atmospheric gas) is used will be described.

[0057] As shown in Figure 7A, the surface of the member 200 has a metal element (M) and fluorine (F). The metal element (M) will be described as, for example, the metal of the member 200 (e.g., Al, etc.), but is not limited to this and may be yttrium (Y) or silicon (Si) of a thermally sprayed film. The metal element (M) is polarized to δ+, and fluorine (F) is polarized to δ-. In addition, H ２ By generating O plasma, active species (protons, hydroxyl groups, oxygen ions, etc.) are generated as shown in the following reaction formula (2). Therefore, fluorine (F), which is polarized to δ- due to its electronegativity, reacts with H, which is polarized to δ+. ＋ is attracted (see reference numeral 321).

[0058] H ２ O → [H ＋ ]+[OH － ]+[O － ]+…… ・・・(2)

[0059] As shown in FIG. 7B, a metal element (M) polarized to δ+ due to electronegativity has OH atoms polarized to δ-. － is attracted (see reference numeral 322). Then, the bond between the metal element (M) and fluorine (F) is broken (see reference numeral 323), and the metal element (M) is converted to OH. － (See reference numeral 324.) Fluorine (F) reacts with H ＋ and reacts.

[0060] As a result, a bond (M-OH) between the metal element (M) and OH is formed as shown in Fig. 7C, and HF gas is also generated.

[0061] Here, dry air and N ２ When the plasma processing chamber 10 is opened after repeated purging processes using a gas, a fluorine-containing gas (e.g., HF gas) may be detected. Therefore, a method of reducing the amount of HF when the plasma processing chamber 10 is opened by increasing the number of repeated purging processes is considered. In this case, the time until the plasma processing chamber 10 is opened becomes longer, and the period of time during which the plasma processing apparatus 1 is stopped becomes longer.

[0062] In contrast, the first processing method shown in Figures 2, 4A to 4C, and 6A to 6C and the second processing method shown in Figures 3, 5A to 5C, and 7A to 7C can efficiently exhaust fluorine-containing gas (e.g., HF gas). This also shortens the time required to open the plasma processing chamber 10, shortening the downtime of the plasma processing apparatus 1. This also improves the productivity of the plasma processing apparatus 1.

[0063] Furthermore, the generated fluorine-containing gas (e.g., HF gas) can be exhausted from the plasma processing chamber 10 by the exhaust system 40 and appropriately treated. That is, the amount of fluorine-containing gas (e.g., HF gas) released into the atmosphere can be sufficiently suppressed.

[0064] Although the gas containing hydrogen (H) and oxygen (O) introduced into plasma processing chamber 10 in step S104 has been described as being supplied from gas supply unit 20, this is not limiting. A check valve, a filter, and an on-off valve may be provided, and atmospheric air containing moisture may be introduced into plasma processing chamber 10 by utilizing the pressure difference between the atmospheric pressure outside plasma processing chamber 10 and the vacuum atmosphere inside plasma processing chamber 10. Furthermore, the atmospheric air introduction is preferably provided at gas exhaust port 10e upstream of the pressure control valve (APC valve) of exhaust system 40.

[0065] [Plasma Processing System] Next, another configuration example of a plasma processing system will be described. Fig. 8 is an example of a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus (substrate processing apparatus) 1 according to a second embodiment.

[0066] A sidewall 10a of the plasma processing chamber 10 is provided with a plurality of gas outlets 24 for introducing a gas containing hydrogen (H) and oxygen (O) into the plasma processing space 10s.

[0067] The gas supply 25 may include at least one gas source 26 and at least one flow controller 27. In one embodiment, the gas supply 25 is configured to supply a gas containing hydrogen (H) and oxygen (O) to the gas outlet 24 via the flow controller 27.

[0068] 9 is a horizontal cross-sectional view showing an example of the arrangement of gas discharge units 24. Gas discharge units 24 discharge gas in the tangential direction of an imaginary circle 400 concentric with plasma processing chamber 10. This forms a swirling flow 410.

[0069] In this way, by supplying gas containing hydrogen (H) and oxygen (O) in a swirling flow, the flow rate of the gas near the side wall 10 a can be increased, and a sufficient amount of gas can be supplied to areas that are difficult for the gas to reach, such as the upper part of the side wall 10 a.

[0070] Furthermore, the HF gas generated from the sidewall 10a, etc., can be exhausted to the outside of the plasma processing chamber 10 by the next swirling flow. That is, the evacuation process shown in step S106 may be omitted. In other words, the step of supplying a gas containing hydrogen and oxygen by a swirling flow (S104) and the step of maintaining the pressure in the plasma processing chamber 10 (S105) may be repeated a predetermined number of times. Furthermore, the step of supplying a gas containing hydrogen and oxygen by a swirling flow (S104) and the step of generating plasma in the plasma processing chamber 10 (S105A) may be repeated a predetermined number of times.

[0071] This allows for efficient exhaust of fluorine-containing gas (e.g., HF gas), shortening the time required to open the plasma processing chamber 10 and shortening the downtime of the plasma processing apparatus 1. Furthermore, the productivity of the plasma processing apparatus 1 can be improved.

[0072] Furthermore, the generated fluorine-containing gas (e.g., HF gas) can be exhausted from the plasma processing chamber 10 by the exhaust system 40 and appropriately treated. That is, the amount of fluorine-containing gas (e.g., HF gas) released into the atmosphere can be sufficiently suppressed.

[0073] The embodiments disclosed above include, for example, the following aspects. (Supplementary Note 1) A processing method for opening a processing chamber of a substrate processing apparatus that processes a substrate using a processing gas containing fluorine, comprising: supplying a gas containing hydrogen and oxygen into the processing chamber; exhausting the gas in the processing chamber after supplying the gas containing hydrogen and oxygen; repeating the steps of supplying the gas containing hydrogen and oxygen and exhausting the gas in the processing chamber; and, after the repeating step, bringing the interior of the processing chamber to atmospheric pressure. (Supplementary Note 2) The processing method according to Supplementary Note 1, further comprising, after the step of supplying the gas containing hydrogen and oxygen and before the step of exhausting the gas in the processing chamber, maintaining the interior of the processing chamber at a predetermined pressure, the repeating step repeats the steps of supplying the gas containing hydrogen and oxygen, maintaining the interior of the processing chamber at a predetermined pressure, and exhausting the gas in the processing chamber. (Supplementary Note 3) The gas containing hydrogen and oxygen is H ２ O, H ２ O ２ , or a polarized alcohol. (Supplementary Note 4) The processing method according to Supplementary Note 2 or Supplementary Note 3, wherein the step of maintaining the interior of the processing chamber at a predetermined pressure comprises maintaining the pressure in the processing chamber at a pressure of 10 Torr or more for a holding time of 1 to 10 minutes. (Supplementary Note 5) The processing method according to Supplementary Note 1, further comprising the step of generating plasma of the gas containing hydrogen and oxygen in the processing chamber after the step of supplying the gas containing hydrogen and oxygen and before the step of exhausting the gas in the processing chamber, and wherein the repeating step repeats the steps of supplying the gas containing hydrogen and oxygen, generating the plasma in the processing chamber, and exhausting the gas in the processing chamber. (Supplementary Note 6) The gas containing hydrogen and oxygen is H ２ O, H ２ O ２ , polar alcohols, H ２ Gas and O ２ Gas mixture, hydrocarbon gas, O ２the processing chamber includes a gas mixture of hydrogen and oxygen, or a mixture of hydrogen and oxygen. (Supplementary Note 7) The processing method according to any one of Supplementary Notes 1 to 6, further comprising the step of supplying a purge gas into the processing chamber to purge the gas in the processing chamber before the step of supplying the gas containing hydrogen and oxygen. (Supplementary Note 8) The processing method according to any one of Supplementary Notes 1 to 7, wherein the step of supplying the gas containing hydrogen and oxygen generates a swirling flow in the processing chamber. (Supplementary Note 9) A processing method for opening a processing chamber of a substrate processing apparatus that processes a substrate using a fluorine-containing processing gas, comprising the steps of: supplying a gas containing hydrogen and oxygen into the processing chamber to generate a swirling flow in the processing chamber; maintaining the processing chamber at a predetermined pressure after the step of supplying the gas containing hydrogen and oxygen; repeating the steps of supplying the gas containing hydrogen and oxygen and maintaining the processing chamber at a predetermined pressure; and, after the repeating step, bringing the processing chamber to atmospheric pressure. (Supplementary Note 10) A processing method for opening a processing chamber of a substrate processing apparatus that processes a substrate using a processing gas containing fluorine, comprising: a step of supplying a gas containing hydrogen and oxygen into the processing chamber to generate a swirling flow in the processing chamber; a step of generating plasma of the gas containing hydrogen and oxygen in the processing chamber after the step of supplying the gas containing hydrogen and oxygen; a step of repeating the step of supplying the gas containing hydrogen and oxygen and the step of generating the plasma in the processing chamber; and a step of setting the pressure in the processing chamber to atmospheric pressure after the step of repeating.(Supplementary Note 11) A substrate processing apparatus comprising: a substrate support part that supports a substrate; a processing chamber that houses the substrate support part; a gas supply part that supplies gas into the processing chamber; an exhaust system that exhausts the gas from the processing chamber; and a control part, wherein the substrate is processed using a processing gas containing fluorine, and the control part controls: via the gas supply part: a step of supplying a gas containing hydrogen and oxygen into the processing chamber; via the exhaust system: a step of exhausting the gas in the processing chamber after supplying the gas containing hydrogen and oxygen; via the gas supply part and the exhaust system: a step of repeating the step of supplying the gas containing hydrogen and oxygen and the step of exhausting the gas in the processing chamber; and via the gas supply part and the exhaust system: a step of setting the pressure in the processing chamber to atmospheric pressure after the repeating step. (Supplementary Note 12) The substrate processing apparatus according to Supplementary Note 11, wherein the control unit controls the gas supply unit and the exhaust system to maintain the interior of the processing chamber at a predetermined pressure after the step of supplying the gas containing hydrogen and oxygen and before the step of exhausting the gas in the processing chamber, and the repeating step repeats the step of supplying the gas containing hydrogen and oxygen, the step of maintaining the interior of the processing chamber at a predetermined pressure, and the step of exhausting the gas in the processing chamber. (Supplementary Note 13) The gas containing hydrogen and oxygen is H. ２ O, H ２ O ２, or a polarized alcohol. (Supplementary Note 14) The substrate processing apparatus according to Supplementary Note 12 or Supplementary Note 13, wherein the step of maintaining the interior of the processing chamber at a predetermined pressure comprises maintaining the pressure in the processing chamber at a pressure of 10 Torr or more for a holding time of 1 to 10 minutes. (Supplementary Note 15) The substrate processing apparatus according to Supplementary Note 11, further comprising, after the step of supplying the gas containing hydrogen and oxygen and before the step of exhausting the gas in the processing chamber, a step of generating plasma of the gas containing hydrogen and oxygen in the processing chamber, and the repeating step comprises repeating the steps of supplying the gas containing hydrogen and oxygen, generating the plasma in the processing chamber, and exhausting the gas in the processing chamber. (Supplementary Note 16) The gas containing hydrogen and oxygen is H ２ O, H ２ O ２ , polar alcohols, H ２ Gas and O ２ Gas mixture, hydrocarbon gas, O ２The substrate processing apparatus according to any one of Appendix 15 to Appendix 17, further comprising the step of supplying a purge gas into the processing chamber to purge the gas in the processing chamber before the step of supplying the gas containing hydrogen and oxygen by the gas supply unit and the exhaust system. (Additional Note 18) The substrate processing apparatus according to any one of Appendix 11 to Appendix 17, further comprising the step of supplying a purge gas into the processing chamber to purge the gas in the processing chamber before the step of supplying the gas containing hydrogen and oxygen by the gas supply unit and the exhaust system. (Supplementary Note 19) A substrate processing apparatus comprising: a substrate support part that supports a substrate; a processing chamber that houses the substrate support part; a gas supply part that supplies gas into the processing chamber; an exhaust system that exhausts the gas from the processing chamber; and a control part, wherein the substrate is processed using a processing gas containing fluorine, wherein the control part controls: using the gas supply part to control a step of supplying a gas containing hydrogen and oxygen into the processing chamber to generate a swirling flow in the processing chamber; using the gas supply part and the exhaust system to control a step of maintaining the interior of the processing chamber at a predetermined pressure after the step of supplying the gas containing hydrogen and oxygen; using the gas supply part and the exhaust system to control a step of repeating the step of supplying the gas containing hydrogen and oxygen and the step of maintaining the interior of the processing chamber at a predetermined pressure; and using the gas supply part and the exhaust system to control a step of setting the interior of the processing chamber at atmospheric pressure after the repeating step.

[0074] The present invention is not limited to the configurations described in the above embodiments, but may be combined with other elements, etc. These aspects can be changed without departing from the spirit of the present invention, and can be appropriately determined depending on the application form.

[0075] This application claims priority based on Japanese Patent Application No. 2024-134054, filed on August 9, 2024, the entire contents of which are incorporated herein by reference.

[0076] 200 Member 210 Reaction layer 211 Hydrogen termination 220 Gas containing hydrogen and oxygen 251 HF gas 1 Plasma processing apparatus 2 Control unit 10 Plasma processing chamber 10a Side wall 10s Plasma processing space 11 Substrate support unit 20 Gas supply unit 30 Power supply 40 Exhaust system 200 Member 210 Reaction layer 211 Hydrogen termination 220 Gas containing hydrogen and oxygen 230 Plasma 251 HF gas W Substrate

Claims

1. A processing method for opening a processing chamber of a substrate processing apparatus that processes a substrate using a processing gas containing fluorine, comprising: a step of supplying a gas containing hydrogen and oxygen into the processing chamber; a step of evacuating the gas in the processing chamber after supplying the gas containing hydrogen and oxygen; a step of repeating the step of supplying the gas containing hydrogen and oxygen and the step of evacuating the gas in the processing chamber; and a step of setting the pressure inside the processing chamber to atmospheric pressure after the repeating step.

2. The processing method according to claim 1, further comprising the step of maintaining the interior of the processing chamber at a predetermined pressure after the step of supplying the gas containing hydrogen and oxygen and before the step of exhausting the gas in the processing chamber, wherein the repeating step repeats the steps of supplying the gas containing hydrogen and oxygen, maintaining the interior of the processing chamber at a predetermined pressure, and exhausting the gas in the processing chamber.

3. The gas containing hydrogen and oxygen is H ２ O, H ２ O ２ 3. The method according to claim 2, wherein the solvent contains any one of alcohols having polarity.

4. The processing method according to claim 2 or 3, wherein the step of maintaining the interior of the processing chamber at a predetermined pressure comprises maintaining the pressure within the processing chamber at a pressure of 10 Torr or more for a holding time within the range of 1 to 10 minutes.

5. The processing method according to claim 1, further comprising the step of generating a plasma of the gas containing hydrogen and oxygen in the processing chamber after the step of supplying the gas containing hydrogen and oxygen and before the step of exhausting the gas in the processing chamber, wherein the repeating step repeats the steps of supplying the gas containing hydrogen and oxygen, generating the plasma in the processing chamber, and exhausting the gas in the processing chamber.

6. The gas containing hydrogen and oxygen is H ２ O, H ２ O ２ , polar alcohols, H ２ Gas and O ２ Gas mixture, hydrocarbon gas, O ２ 6. The method of claim 5, wherein the gas mixture comprises either:

7. The processing method according to claim 1, further comprising the step of supplying a purge gas into the processing chamber to purge the gas in the processing chamber before the step of supplying the gas containing hydrogen and oxygen.

8. The processing method according to claim 1, wherein the step of supplying a gas containing hydrogen and oxygen generates a swirling flow in the processing chamber.

9. A processing method for opening a processing chamber of a substrate processing apparatus that processes a substrate using a processing gas containing fluorine, comprising: a step of supplying a gas containing hydrogen and oxygen into the processing chamber to generate a swirling flow in the processing chamber; a step of maintaining the interior of the processing chamber at a predetermined pressure after the step of supplying the gas containing hydrogen and oxygen; a step of repeating the step of supplying the gas containing hydrogen and oxygen and the step of maintaining the interior of the processing chamber at a predetermined pressure; and a step of setting the interior of the processing chamber to atmospheric pressure after the step of repeating.

10. A processing method for opening a processing chamber of a substrate processing apparatus that processes a substrate using a processing gas containing fluorine, comprising: a step of supplying a gas containing hydrogen and oxygen into the processing chamber and generating a swirling flow in the processing chamber; a step of generating plasma of the gas containing hydrogen and oxygen in the processing chamber after the step of supplying the gas containing hydrogen and oxygen; a step of repeating the step of supplying the gas containing hydrogen and oxygen and the step of generating the plasma in the processing chamber; and a step of setting the pressure in the processing chamber to atmospheric pressure after the step of repeating.

11. A substrate processing apparatus comprising: a substrate support part for supporting a substrate; a processing chamber accommodating the substrate support part; a gas supply part for supplying gas into the processing chamber; an exhaust system for exhausting the gas from the processing chamber; and a control part, wherein the substrate is processed using a processing gas containing fluorine, and the control part controls: via the gas supply part: a step of supplying a gas containing hydrogen and oxygen into the processing chamber; via the exhaust system: a step of exhausting the gas in the processing chamber after supplying the gas containing hydrogen and oxygen; via the gas supply part and the exhaust system: a step of repeating the step of supplying the gas containing hydrogen and oxygen and the step of exhausting the gas in the processing chamber; and via the gas supply part and the exhaust system: a step of setting the pressure in the processing chamber to atmospheric pressure after the repeating step.

12. The substrate processing apparatus of claim 11, wherein the control unit controls the gas supply unit and the exhaust system to maintain the interior of the processing chamber at a predetermined pressure after the step of supplying the gas containing hydrogen and oxygen and before the step of exhausting the gas in the processing chamber, and the repeating step repeats the step of supplying the gas containing hydrogen and oxygen, the step of maintaining the interior of the processing chamber at a predetermined pressure, and the step of exhausting the gas in the processing chamber.

13. The gas containing hydrogen and oxygen is H ２ O, H ２ O ２ The substrate processing apparatus according to claim 12 , wherein the solvent contains any one of alcohols having polarity.

14. The substrate processing apparatus according to claim 12 or 13, wherein the step of maintaining the interior of the processing chamber at a predetermined pressure comprises maintaining the pressure within the processing chamber at a pressure of 10 Torr or more for a holding time within a range of 1 to 10 minutes.

15. The substrate processing apparatus according to claim 11, further comprising the step of generating a plasma of the gas containing hydrogen and oxygen in the processing chamber after the step of supplying the gas containing hydrogen and oxygen and before the step of exhausting the gas in the processing chamber, wherein the repeating step repeats the steps of supplying the gas containing hydrogen and oxygen, generating the plasma in the processing chamber, and exhausting the gas in the processing chamber.

16. The gas containing hydrogen and oxygen is H ２ O, H ２ O ２ , polar alcohols, H ２ Gas and O ２ Gas mixture, hydrocarbon gas, O ２ 16. The substrate processing apparatus of claim 15, wherein the substrate processing apparatus comprises either a gas mixture or a gas mixture.

17. The substrate processing apparatus according to claim 11, further comprising the step of supplying a purge gas into the processing chamber to purge the gas in the processing chamber before the step of supplying the gas containing hydrogen and oxygen by the gas supply unit and the exhaust system.

18. The substrate processing apparatus according to claim 11, wherein the step of supplying the gas containing hydrogen and oxygen generates a swirling flow in the processing chamber.

19. A substrate processing apparatus comprising: a substrate support part for supporting a substrate; a processing chamber accommodating the substrate support part; a gas supply part for supplying gas into the processing chamber; an exhaust system for exhausting the gas from the processing chamber; and a control part, wherein the substrate is processed using a processing gas containing fluorine, and the control part controls: using the gas supply part to control a step of supplying a gas containing hydrogen and oxygen into the processing chamber and generating a swirling flow in the processing chamber; using the gas supply part and the exhaust system to control a step of maintaining the interior of the processing chamber at a predetermined pressure after the step of supplying the gas containing hydrogen and oxygen; using the gas supply part and the exhaust system to control a step of repeating the step of supplying the gas containing hydrogen and oxygen and the step of maintaining the interior of the processing chamber at a predetermined pressure; and using the gas supply part and the exhaust system to control a step of setting the interior of the processing chamber to atmospheric pressure after the repeating step.

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