Plasma processing method and plasma processing apparatus

Abstract

In a plasma processing method, (a) a substrate is provided having a first region comprising a first material and a second region comprising a second material different from the first material. And (b) supplying a modifying gas and a carbon-containing precursor for modifying the surface of the first region. And (c) forming a modified layer by modifying the surface of the first region with plasma generated from a mixed gas containing a modifying gas and a carbon-containing precursor by supplying a first high-frequency power. And (d) removing the modified layer by reacting the modified layer with the carbon-containing precursor by stopping the supply of the first high-frequency power or supplying a second high-frequency power that is smaller than the first high-frequency power.

Description

Technical Field

[0001] Exemplary embodiments of the present invention relate to a plasma processing method and a plasma processing apparatus. Background Art

[0002] Patent Document 1 discloses an atomic layer etching (ALE) method. In this method, a substrate is exposed to a hydrogen fluoride gas to form a fluorinated surface layer on a metal oxide film. Then, the substrate is exposed to a boron-containing gas to remove the fluorinated surface layer from the metal oxide film.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent document 1: Japanese Patent Application Publication No. 2018-26566. Summary of the invention

[0006] Problem that the invention aims to solve

[0007] The present invention provides a plasma processing method and a plasma processing apparatus capable of achieving high productivity.

[0008] Technical solutions to the problem

[0009] In an exemplary embodiment, a plasma treatment method includes: (a) providing a substrate having a first region containing a first material and a second region containing a second material different from the first material; (b) supplying a modifying gas and a carbon-containing precursor for modifying a surface of the first region; (c) modifying the surface of the first region to form a modified layer using plasma generated from a mixed gas containing the modifying gas and the carbon-containing precursor by supplying a first high-frequency power; and (d) stopping supplying the first high-frequency power or supplying a second high-frequency power that is smaller than the first high-frequency power to allow the modified layer to react with the carbon-containing precursor, thereby removing the modified layer.

[0010] Effects of the Invention

[0011] According to an exemplary embodiment, a plasma processing method and a plasma processing apparatus that can achieve high productivity are provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 FIG. 1 is a diagram schematically showing a plasma processing apparatus according to an exemplary embodiment.

[0013] Figure 2 FIG. 1 is a diagram schematically showing a plasma processing apparatus according to an exemplary embodiment.

[0014] Figure 3 is a flow chart of a plasma processing method according to an exemplary embodiment.

[0015] Figure 4 It can be applied Figure 3 A cross-sectional view of a substrate according to an example of the method.

[0016] Figure 5 is a cross-sectional view of a substrate in an example of a process of a plasma processing method according to an exemplary embodiment.

[0017] Figure 6 is a cross-sectional view of a substrate in an example of a process of a plasma processing method according to an exemplary embodiment.

[0018] Figure 7 is a cross-sectional view of a substrate in an example of a process of a plasma processing method according to an exemplary embodiment.

[0019] Figure 8 FIG. 1 is a timing chart showing an example of time changes in high frequency power and bias power supplied to a plasma processing apparatus.

[0020] Fig. 9 FIG. 1 is a timing chart showing another example of the temporal changes of the high frequency power and the bias power supplied to the plasma processing apparatus.

[0021] Fig.10 FIG. 1 is a timing chart showing another example of the temporal changes of the high frequency power and the bias power supplied to the plasma processing apparatus.

[0022] Fig.11 is a cross-sectional view showing an etching device included in a plasma processing apparatus according to an exemplary embodiment.

[0023] Fig.12 FIG. 1 is a diagram showing a plasma processing apparatus according to an exemplary embodiment. DETAILED DESCRIPTION

[0024] Various exemplary embodiments (1) to (15) are described below.

[0025] (1) A plasma treatment method comprises: (a) providing a substrate having a first region comprising a first material and a second region comprising a second material different from the first material; (b) supplying a modifying gas and a carbon-containing precursor for modifying the surface of the first region; (c) modifying the surface of the first region to form a modified layer using plasma generated from a mixed gas comprising the modifying gas and the carbon-containing precursor by supplying a first high-frequency power; and (d) stopping supplying the first high-frequency power or supplying a second high-frequency power that is smaller than the first high-frequency power to allow the modified layer to react with the carbon-containing precursor, thereby removing the modified layer.

[0026] According to the above plasma processing method, by controlling the supply of high frequency power, the formation of the modified layer and the removal of the modified layer can be switched. Between (c) and (d), there is no need to purge the gas. Therefore, high productivity can be achieved.

[0027] (2) In the above (1), the first region may include a metal-containing film, and the second region may include a mask. In this case, the metal-containing film can be etched using the mask.

[0028] (3) In the above (1) or (2), the carbon-containing precursor may not contain metal. In this case, in (c), even if the carbon-containing precursor in the plasma is dissociated, no metal derived from the carbon-containing precursor is generated, thereby suppressing metal contamination of the substrate.

[0029] (4) In the above (3), the carbon-containing precursor may include at least one of alcohol, β-diketone, amidine, acetoamidine and β-ketodiimine.

[0030] (5) In any one of the above (1) to (4), the reforming gas and the carbon-containing precursor may be continuously supplied during the period including the steps (c) and (d). In this case, the formation and removal of the reformed layer can be performed continuously.

[0031] (6) In any one of (1) to (5) above, the plasma processing method may further include (e) repeatedly performing the steps (c) and (d). In this case, the etching amount of the first region can be increased.

[0032] (7) In any one of the above (1) to (6), the substrate may be heated in (d). In this case, the reaction between the modified layer and the carbon-containing precursor can be promoted.

[0033] (8) In any one of the above (1) to (7), the reforming gas may contain at least one of a halogen-containing gas and an oxygen-containing gas.

[0034] (9) In any one of the above (1) to (8), the modifying gas may contain at least one of a fluorine-containing gas and a chlorine-containing gas.

[0035] (10) In any of the above (1) to (9), the modified gas may contain at least one selected from fluorocarbon gas, HF gas, NF3 gas, SF6 gas, chlorocarbon gas, Cl2 gas, NCl3 gas, SCl6 gas, O2 gas, CO gas and CO2 gas.

[0036] (11) In any one of the above (1) to (10), in the step (d), supply of the first high-frequency power may be stopped so that plasma is not generated.

[0037] (12) In any one of the above (1) to (11), in (c), a carbonaceous deposit may be formed on the second region. In this case, the second region can be protected by the carbonaceous deposit.

[0038] (13) In any of the above (1) to (12), in (c), bias power may be supplied to an electrode in a substrate supporter supporting the substrate. In this case, ions originating from the modified gas in the plasma are introduced to the surface of the first region, thereby promoting the formation of the modified layer.

[0039] (14) In the above (13), the period during which the bias power is supplied is shorter than the period during which the first high-frequency power is supplied. In this case, during the period during which the bias power is not supplied, the formation of the carbon-containing deposit on the second region is promoted.

[0040] (15) In the above (13) or (14), the bias power may include a first bias power and a second bias power greater than the first bias power. In this case, while the first bias power is supplied, the formation of the carbonaceous deposit on the second region is promoted. While the second bias power is supplied, the formation of the modified layer is promoted.

[0041] (16) The plasma treatment method includes: (a) providing a substrate having a metal-containing film and a mask on the metal-containing film; (b) supplying a modifying gas and a carbon-containing precursor for modifying the surface of the metal-containing film; (c) modifying the surface of the metal-containing film to form a modified layer using plasma generated from a mixed gas containing the modifying gas and the carbon-containing precursor by supplying a first high-frequency power; and (d) stopping supplying the first high-frequency power to allow the modified layer to react with the carbon-containing precursor, thereby removing the modified layer.

[0042] (17) A plasma processing method comprises: (a) providing a substrate on a substrate support comprising an electrode, wherein the substrate has a first region comprising a metal and a second region comprising an element other than the metal; (b) supplying a gas comprising at least one of a halogen and oxygen and a carbon-containing precursor; and (c) removing the first region, wherein (c) comprises: (c1) a first period during which a first high-frequency power is supplied; and (c2) a second period alternating with the first period, wherein the first high-frequency power is not supplied or a second high-frequency power smaller than the first high-frequency power is supplied during the second period.

[0043] (18) In the above (17), the first high-frequency power and the second high-frequency power are high-frequency powers for plasma generation.

[0044] (19) A plasma processing apparatus comprises: a chamber; a substrate support for supporting a substrate in the chamber, the substrate having a first region containing a first material and a second region containing a second material different from the first material; a gas supply unit configured to supply a modifying gas and a carbon-containing precursor for modifying a surface of the first region into the chamber; a plasma generating unit configured to generate plasma from a mixed gas containing the modifying gas and the carbon-containing precursor by supplying a first high-frequency power in the chamber; and a control unit configured to control the gas supply unit and the plasma generating unit to perform the following steps: modifying the surface of the first region using the plasma to form a modified layer; and stopping supplying the first high-frequency power or supplying a second high-frequency power that is smaller than the first high-frequency power to allow the modified layer to react with the carbon-containing precursor, thereby removing the modified layer.

[0045] Hereinafter, various exemplary embodiments will be described in detail with reference to the accompanying drawings. In addition, in each of the drawings, the same reference numerals are given to the same or corresponding parts.

[0046] Figure 1: is a diagram for illustrating a structural example of a plasma processing system. In one embodiment, the plasma processing system includes a plasma processing device 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing device 1 is an example of a substrate processing device. The plasma processing device 1 includes a plasma processing chamber 10, a substrate support portion 11, and a plasma generating portion 12. The plasma processing chamber 10 has a plasma processing space. In addition, the plasma processing chamber 10 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 the gas supply portion 20 described later, and the gas exhaust port is connected to the exhaust system 40 described later. The substrate support portion 11 is arranged in the plasma processing space and has a substrate supporting surface for supporting a substrate.

[0047] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be a capacitively coupled plasma (CCP: Capacitively Coupled Plasma), an inductively coupled plasma (ICP: Inductively Coupled Plasma), an ECR plasma (Electron-Cyclotron-Resonance Plasma), a helicon wave excited plasma (HWP: Helicon Wave Plasma) or a surface wave plasma (SWP: Surface Wave Plasma), etc. In addition, various types of plasma generating units including an AC (Alternating Current: Alternating Current) plasma generating unit and a DC (Direct Current: Direct Current) plasma generating unit may also be used. In one embodiment, the AC signal (AC power) used in the AC plasma generating unit has a frequency in the range of 100kHz to 10GHz. Therefore, the AC signal includes an RF (Radio Frequency: High Frequency) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100kHz to 150MHz.

[0048] The control unit 2 processes computer executable commands that enable the plasma processing device 1 to perform various processes described in the present invention. The control unit 2 can be configured to control the various elements of the plasma processing device 1 to perform the various processes described herein. In one embodiment, a part or all of the control unit 2 can be included in the plasma processing device 1. The control unit 2 can include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. The control unit 2 is implemented, for example, by a computer 2a. The processing unit 2a1 can be configured to perform various control operations by reading a program from the storage unit 2a2 and executing the read program. The program can be pre-stored in the storage unit 2a2, or it can be obtained via a medium when necessary. The obtained program is stored in the storage unit 2a2, and is read and executed from the storage unit 2a2 by the processing unit 2a1. The medium can be various storage media readable by the computer 2a, or it can be a communication line connected to the communication interface 2a3. The processing unit 2a1 can be a CPU (Central Processing Unit: Central Processing Unit). The storage unit 2a2 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 2a3 may communicate with the plasma processing apparatus 1 via a communication line such as a LAN (Local Area Network).

[0049] Hereinafter, a configuration example of a capacitive coupling type plasma processing apparatus will be described as an example of the plasma processing apparatus 1 . Figure 2 It is a diagram for explaining a configuration example of a capacitive coupling type plasma processing apparatus.

[0050] A capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power supply 30, and an exhaust system 40. In addition, the plasma processing apparatus 1 includes a substrate support unit 11 and a gas introduction unit. The gas introduction unit is configured to be able to introduce at least one processing gas into the plasma processing chamber 10. The gas introduction unit includes a shower head 13. The substrate support unit 11 is arranged in the plasma processing chamber 10. The shower head 13 is arranged above the substrate support unit 11. In one embodiment, the shower head 13 constitutes at least a portion of the top (ceiling) of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the shower head 13, the side wall 10a of the plasma processing chamber 10, and the substrate support unit 11. The plasma processing chamber 10 is grounded. The shower head 13 and the substrate support unit 11 are electrically insulated from the shell of the plasma processing chamber 10.

[0051] The substrate support portion 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 when viewed from above. The substrate W is arranged on the central region 111a of the main body 111, and the ring assembly 112 is arranged on the annular region 111b of the main body 111 in a manner of surrounding the substrate W on the central region 111a of the main body 111. Therefore, the central region 111a is also referred to as a substrate support surface for supporting the substrate W, and the annular region 111b is also referred to as a ring support surface for supporting the ring assembly 112.

[0052] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive component. The conductive component of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is arranged on the base 1110. The electrostatic chuck 1111 includes a ceramic component 1111a and an electrostatic electrode 1111b arranged in the ceramic component 1111a. The ceramic component 1111a has a central area 111a. In one embodiment, the ceramic component 1111a also has an annular area 111b. In addition, other components surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating component, may have an annular area 111b. In this case, the ring assembly 112 may be arranged on the annular electrostatic chuck or the annular insulating component, or on both the electrostatic chuck 1111 and the annular insulating component. In addition, at least one RF / DC electrode coupled to the RF power supply 31 and / or DC power supply 32 described later may also be arranged in the ceramic component 1111a. In this case, at least one RF / DC electrode functions as a lower electrode. In the case where the bias RF signal and / or DC signal described later is supplied to at least one RF / DC electrode, the RF / DC electrode may also be referred to as a bias electrode. In addition, the conductive component of the base 1110 and at least one RF / DC electrode may also function as a plurality of lower electrodes. In addition, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support portion 11 includes at least one lower electrode.

[0053] The ring assembly 112 includes one or more ring-shaped components. In one embodiment, the one or more ring-shaped components include one or more edge rings and at least one cover ring. The edge ring is formed of a conductive material or an insulating material, and the cover ring is formed of an insulating material.

[0054] In addition, the substrate support portion 11 may include a temperature adjustment module for adjusting 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 path 1110a or a combination thereof. A heat transfer fluid such as salt water or gas flows in the flow path 1110a. In one embodiment, the flow path 1110a is formed in the base 1110, and one or more heaters are arranged in the ceramic part 1111a of the electrostatic chuck 1111. In addition, the substrate support portion 11 may include a heat transfer gas supply portion configured to supply a heat transfer gas to the gap between the back side of the substrate W and the central area 111a.

[0055] The showerhead 13 is configured to be able to introduce at least one processing gas from the gas supply unit 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b and a plurality of gas introduction ports 13c. The processing gas supplied to the gas supply port 13a is introduced into the plasma processing space 10s from the plurality of gas introduction ports 13c through the gas diffusion chamber 13b. In addition, the showerhead 13 includes at least one upper electrode. In addition, in addition to the showerhead 13, the gas introduction unit may also include one or more side gas injection units (SGI: Side Gas Injector), which are installed in one or more openings formed on the side wall 10a.

[0056] The gas supply unit 20 may further 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 processing gas from the corresponding gas source 21 to the shower head 13 via the corresponding flow controller 22. Each flow controller 22 may also include, for example, a mass flow controller or a pressure-controlled flow controller. In addition, the gas supply unit 20 may further include at least one flow modulation device for modulating or pulsing the flow of at least one processing gas.

[0057] 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. Thus, plasma is formed 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 generating unit 12. In addition, by supplying a bias RF signal to at least one lower electrode, a bias potential can be generated on the substrate W, and ion components in the formed plasma can be introduced into the substrate W.

[0058] In one embodiment, the RF power supply 31 includes a first RF generator 31a and a second RF generator 31b. The first RF generator 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 generation source RF signal (generation source RF power) for plasma generation. In one embodiment, the generation source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generator 31a may also be configured to generate a plurality of generation source RF signals having different frequencies. The generated one or more generation source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0059] The second RF generating unit 31b is coupled to at least one lower electrode via at least one impedance matching circuit, and is configured to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the generating source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the generating source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100kHz to 60MHz. In one embodiment, the second RF generating unit 31b may also be configured to generate a plurality of bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. In addition, in various embodiments, at least one of the generating source RF signal and the bias RF signal may also be pulsed.

[0060] In addition, the power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generating unit 32a and a second DC generating unit 32b. In one embodiment, the first DC generating unit 32a is connected to at least one lower electrode and is configured to generate a first DC signal. The generated first DC signal is applied to at least one lower electrode. In one embodiment, the second DC generating unit 32b is connected to at least one upper electrode and is configured to generate a second DC signal. The generated second DC signal is applied to at least one upper electrode.

[0061] In various embodiments, the first and second DC signals may also 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 pulse may have a pulse waveform of a rectangle, a trapezoid, a triangle, or a combination thereof. In one embodiment, a waveform generator for generating a sequence of voltage pulses from a DC signal is connected between the first DC generator 32a and at least one lower electrode. Therefore, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. In the case where 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 pulse may have a positive polarity or a negative polarity. In addition, the sequence of voltage pulses may also include one or more positive polarity voltage pulses and one or more negative polarity voltage pulses in one cycle. In addition, the first and second DC generators 32a, 32b may be provided in addition to the RF power supply 31, or the first DC generator 32a may be provided instead of the second RF generator 31b.

[0062] The exhaust system 40 can be connected to a gas outlet 10e provided at the bottom of the plasma processing chamber 10, for example. The exhaust system 40 can also include a pressure regulating valve and a vacuum pump. The pressure in the plasma processing space 10s can be adjusted by the pressure regulating valve. The vacuum pump can include a turbomolecular pump, a dry pump, or a combination thereof.

[0063] The plasma processing apparatus 1 may include a heating device for heating the surface of the substrate W. Fig.11 The etching device 105 shown may have a heating device for heating the surface of the substrate W. The heating device may include, for example, an energy ray generating device. Examples of energy ray generating devices include infrared generating devices, electromagnetic wave generating devices, and laser generating devices. The heating device may be disposed outside the plasma processing chamber 10. In this case, for example, energy rays are irradiated to the substrate W through a window provided on the side wall 10a of the plasma processing chamber 10, so that the surface of the substrate W can be heated. Alternatively, energy rays are irradiated to the substrate W through a shower head 13 formed of a material that is transparent to energy rays, so that the surface of the substrate W can be heated. The heating device may be disposed in the plasma processing chamber 10. In this case, the heating device may have a heater provided in the substrate support portion 11.

[0064] The plasma processing apparatus 1 may include a monitoring device for monitoring the etching amount. Fig.11The etching device 105 shown may have a monitoring device for monitoring the etching amount. The end point of etching can be detected by the monitoring device. The monitoring device may be a light emission analyzer (OES: Optical Emission Spectrometer: direct reading spectrometer) for analyzing plasma light emission. The monitoring device may also be a film thickness meter for measuring the thickness of the film to be etched. Examples of film thickness meters include optical film thickness meters. The film thickness meter may be a linear film thickness meter. The film thickness meter may be disposed outside the plasma processing chamber 10. In one example, it may also be disposed on a conveying path for conveying the etched substrate W (for example, an opening formed in the chamber through which the substrate passes). The monitoring device may be a mass measuring instrument for measuring the mass of the substrate W. Examples of mass measuring instruments include a scale. The mass measuring instrument may be disposed under the substrate support 11.

[0065] Figure 3 is a flow chart of a plasma processing method according to an exemplary embodiment. Figure 3 The plasma processing method MT shown (hereinafter referred to as "method MT") can be performed by the plasma processing device 1 of the above-mentioned embodiment. The method MT can be an etching method. The method MT can also be an atomic layer etching (ALE) method. The method MT can be applied to a substrate W.

[0066] Figure 4 It can be applied Figure 3 A cross-sectional view of a substrate of an example of the method. Figure 4 As shown, in one embodiment, the substrate W includes a first region R1 and a second region R2. The substrate W may include a base region UR. The first region R1 may be disposed on the base region UR. The second region R2 may be disposed on the first region R1.

[0067] The first region R1 includes a first material. The first region R1 may include a metal. The first region R1 may include a metal-containing film. The first region R1 may include at least one of a metal film and a metal compound film. The first region R1 may include at least one of oxygen and nitrogen. The first region R1 may include at least one of a metal oxide and a metal nitride. The first region R1 may include at least one of Al, Hf, Zr, Fe, Ni, Co, Mn, Mg, Rh, Ru, Cr, Si, Ti, Ga, In, Zn, Pb, Ge, Ta, Cu, W, Mo, Pt, Cd, and Sn.

[0068] The second region R2 includes a second material different from the first material. The second region R2 may include an element other than the metal included in the first region R1 (e.g., metal, silicon, or carbon). The second region R2 may include silicon. The second region R2 may include at least one of silicon oxide and silicon nitride. The second region R2 may include carbon. The second region R2 may include at least one of photoresist, spin-on carbon, amorphous carbon, and tungsten carbide. The second region R2 may include a mask. The second region R2 may have an opening OP.

[0069] The base region UR may include a third material different from the first material and the second material. The base region UR may include at least one of silicon, carbon, and metal.

[0070] In the following, regarding the method MT, a case where the method MT is applied to a substrate W using the plasma processing apparatus 1 of the above-mentioned embodiment is taken as an example, and reference is made to Figure 3 to Figure 7 Provide explanation. Figure 5 to Figure 7 1 is a cross-sectional view of a substrate in one example of a process of a plasma processing method according to an exemplary embodiment. When the plasma processing apparatus 1 is used, the method MT can be executed in the plasma processing apparatus 1 by controlling each part of the plasma processing apparatus 1 by the control unit 2. In the method MT, Figure 2 As shown, a substrate W placed on a substrate support 11 (substrate support) in a plasma processing chamber 10 is processed.

[0071] like Figure 3 As shown, method MT may include steps ST1 to ST5. Steps ST1 to ST5 may be performed sequentially. Step ST5 may not be performed. Steps ST3 to ST5 may be performed after step ST2 has been performed. Steps ST1 to ST5 may be performed in-situ. That is, method MT may be performed without taking substrate W out of plasma processing chamber 10.

[0072] In step ST1, provide Figure 4 The substrate W shown. Figure 2 As shown, the substrate W may be provided on the substrate support 11 in the plasma processing chamber 10. The base region UR may be disposed between the substrate support 11 and the first region R1.

[0073] In step ST2, if Figure 5 As shown, a modifying gas MD and a carbon-containing precursor PR are supplied for modifying the surface Ra1 of the first region R1. Figure 2As shown, the modified gas MD and the carbon-containing precursor PR can be supplied from the gas supply unit 20 into the plasma processing chamber 10. The modified gas MD and the carbon-containing precursor PR can be mixed in the plasma processing chamber 10, or can be mixed before being supplied into the plasma processing chamber 10. The modified gas MD and the carbon-containing precursor PR can be supplied into the plasma processing chamber 10 at the same time, or can be supplied with a time difference.

[0074] The modified gas MD may include at least one of a halogen-containing gas and an oxygen-containing gas. The halogen-containing gas can be used when the first region R1 includes at least one of a metal oxide film and a metal nitrogen film. The modified gas MD may include a fluorine-containing gas. The fluorine-containing gas may include at least one of hydrogen fluoride gas (HF gas), a fluorocarbon gas, a nitrogen-containing gas, and a sulfur-containing gas. The fluorocarbon gas may include at least one of C4F6 gas, C4F8 gas, C3F8 gas, and CF4 gas. The nitrogen-containing gas may include NF3 gas. The sulfur-containing gas may include SF6 gas. The modified gas MD may include a chlorine-containing gas. The chlorine-containing gas may include at least one of Cl2 gas, a chlorocarbon gas, a nitrogen-containing gas, and a sulfur-containing gas. The chlorocarbon gas may include at least one of C4Cl6 gas, C4Cl8 gas, C3Cl8 gas, and CCl4 gas. The nitrogen-containing gas may include NCl3 gas. The sulfur-containing gas may include SCl6 gas.

[0075] The oxygen-containing gas can be used when the first region R1 includes a metal film. The oxygen-containing gas may include at least one of O2 gas, CO gas, and CO2 gas.

[0076] The carbon-containing precursor PR may not contain a metal. The carbon-containing precursor PR may contain at least one of an alcohol, a β-diketone, an amidine, an acetoamidine, and a β-ketodiimine. The β-diketone may contain at least one of acac (acetylacetone), hfac (hexafluoroacetylacetone), tfac (trifluoroacetylacetone), and tmhd (tetramethylheptanedione).

[0077] In step ST2, an inert gas may be further supplied. The inert gas may include at least one of a rare gas and N2 gas.

[0078] In step ST3, if Figure 6 As shown, the surface R1a of the first region R1 is modified by plasma PL generated from a mixed gas containing a modified gas MD and a carbon-containing precursor PR to form a modified layer ML. The plasma PL is generated by supplying a first high-frequency power to the plasma processing device 1. In the plasma PL, the modified gas MD is dissociated to generate active species (ions or radicals).

[0079] The modified layer ML can be formed by a reaction between active species generated from the modified gas MD and the first region R1. For example, the modified gas MD may contain a halogen-containing gas, and the first region R1 may contain at least one of a metal oxide film and a metal nitride film. In this case, the modified layer ML can be formed by a reaction between active species generated from the modified gas MD and containing halogen and at least one of the metal oxide film and the metal nitride film.

[0080] In step ST3, a carbon-containing deposit DP may be formed on the second region R2. The carbon-containing deposit DP may be formed from a carbon-containing precursor PR. In the plasma PL, the carbon-containing precursor PR dissociates to generate active species (ions or radicals). Active species generated from the carbon-containing precursor PR and containing carbon are deposited on the second region R2, thereby forming the carbon-containing deposit DP. Since the second region R2 can be protected by the carbon-containing deposit DP, a high etching selectivity ratio for the second region R2 may be obtained in step ST4.

[0081] In step ST3, bias power may be supplied to the electrode in the substrate support portion 11 supporting the substrate W. The bias power may be high frequency power. The bias power introduces ions from the modified gas MD in the plasma PL to the surface R1a of the first region R1, thereby promoting the formation of the modified layer ML.

[0082] In step ST3, the substrate W may be heated. The temperature of the substrate support 11 may be above 100°C, above 150°C, or above 200°C. The temperature of the substrate support 11 may be below 450°C. Heating can be performed by the plasma PL generated in the plasma processing chamber 10 or the temperature adjustment module in the substrate support 11. Heating can be performed by energy rays irradiated from an energy ray generating device. By heating, the reaction between the first region R1 and the modified gas MD is promoted.

[0083] In step ST4, if Figure 7As shown, the supply of the first high-frequency power is stopped so that the modified layer ML reacts with the carbon-containing precursor PR, thereby removing the modified layer ML. Through steps ST3 and ST4, the first region R1 can be removed. The supply of the first high-frequency power can be stopped so that plasma is not generated. In step ST4, a highly volatile by-product BP can be generated by the reaction of the modified layer ML with the carbon-containing precursor PR. The modified layer ML can be removed by volatilization of the by-product BP. By removing the modified layer ML, a recess RS can be formed in the first region R1. In step ST4, a second high-frequency power smaller than the first high-frequency power can be supplied. Even in this case, the by-product BP can be generated by the reaction of the modified layer ML with the carbon-containing precursor PR. Plasma can also be generated by supplying the second high-frequency power. In this case, the by-product BP can be generated by the reaction of the undissociated carbon-containing precursor PR in the plasma with the modified layer ML.

[0084] In step ST4, a mixed gas containing the reforming gas MD and the carbon-containing precursor PR can be supplied. In step ST4, the supply of the reforming gas MD may be stopped, or the reforming gas MD may be supplied at a flow rate smaller than that in step ST3.

[0085] In step ST4, the substrate W may be heated in the same manner as in step ST3. The heating promotes the reaction between the modified layer ML and the carbon-containing precursor PR.

[0086] During the period including step ST3 and step ST4, the modifying gas MD and the carbon-containing precursor PR may be continuously supplied. That is, between step ST3 and step ST4, the switching of the gas type and the gas purging may not be performed. During the period including step ST3 and step ST4, the flow rates of the modifying gas MD and the carbon-containing precursor PR may be constant or may be changed over time.

[0087] In step ST5, step ST3 and step ST4 may be repeated. Step ST3 and step ST4 may be performed alternately. Step ST3 and step ST4 may be repeated multiple times. When the number of executions of step ST3 and step ST4 reaches a threshold, step ST5 may be terminated. Step ST5 can increase the etching amount of the first region R1, thereby forming a deep recess RS.

[0088] According to the method MT, by controlling the supply of high-frequency power in the steps ST3 and ST4, the formation of the modified layer ML and the removal of the modified layer ML can be switched. Between the steps ST3 and ST4, there is no need to switch the gas type from the modified gas MD to the carbon-containing precursor PR and to purge the gas (removal of the modified gas MD). Therefore, the total processing time of the steps ST3 and ST4 can be shortened, so high productivity can be obtained.

[0089] When the carbon-containing precursor PR does not contain metal, even if the carbon-containing precursor PR in the plasma PL is dissociated in step ST3 , metal derived from the carbon-containing precursor PR is not generated, so that metal contamination of the substrate W and the plasma processing chamber 10 can be suppressed.

[0090] Figure 8 1 is a timing chart showing an example of the time variation of the high frequency power and bias power supplied to the plasma processing device. The horizontal axis represents time t and the vertical axis represents the magnitude of the power. Figure 8 The timing diagram is associated with steps S3 to S5 in the method MT. The high-frequency power used to generate the plasma PL in step ST3 may be high-frequency power HF applied to an electrode in the main body 111 of the substrate support 11 or an electrode opposite to the substrate support 11. The frequency of the high-frequency power HF may be greater than 27 MHz and less than 100 MHz. The bias power may be high-frequency power LF applied to an electrode in the main body 111 of the substrate support 11. The frequency of the high-frequency power LF may be smaller than the frequency of the high-frequency power HF. The frequency of the high-frequency power LF may be greater than 100 kHz and less than 40.68 MHz.

[0091] The high-frequency power HF and the high-frequency power LF can be applied periodically with a period CY. That is, the high-frequency power HF and the high-frequency power LF can be pulses, respectively. The period CY can include a first period CY1 and a second period CY2. The second period CY2 is a period after the first period CY1. The second period CY2 can be a period alternating with the first period CY1. The first period CY1 corresponds to step ST3. In the first period CY1, high-frequency power HF for generating plasma PL can be supplied. The second period CY2 corresponds to step ST4. In the second period CY2, high-frequency power HF can be supplied or supplied for generating plasma PL. The high-frequency power HF that can be supplied in the second period CY2 is smaller than the high-frequency power HF supplied in the first period CY1. One cycle corresponding to the period CY can be repeatedly implemented more than 2 times. The process of repeating the period CY corresponds to step ST5. The frequency of the specified period CY can be greater than 0.1 Hz and less than 100 kHz, or can be greater than 10 Hz and less than 100 kHz. The time length of the period CY is the reciprocal of the frequency of the specified period CY.

[0092] During the first period CY1, the high-frequency power LF can be maintained at a high power L2, and the high-frequency power HF can be maintained at a high power H2. During the first period CY1, a modified layer ML and a carbon-containing deposit DP can be formed. During the second period CY2, the high-frequency power LF can be maintained at a low power L1 (for example, 0 W) smaller than the high power L2, and the high-frequency power HF can be maintained at a low power H1 (for example, 0 W) smaller than the high power H2. During the second period CY2, the modified layer ML and the carbon-containing deposit DP are not formed, and the modified layer ML can be removed. Figure 8 In the embodiment, the high frequency power HF and the high frequency power LF may be synchronized pulses.

[0093] Fig. 9 FIG. 1 is a timing chart showing another example of the temporal changes of the high frequency power and the bias power supplied to the plasma processing apparatus. Fig. 9 The timing diagram is similar to that of Figure 8 The timing diagram is the same as Fig. 9 In the timing diagram of , the first period CY1 of the cycle CY may include a third period CY11 and a fourth period CY12. The fourth period CY12 is a period after the third period CY11.

[0094] In the third period CY11, the high-frequency power LF can be maintained at the low power L1, and the high-frequency power HF can be maintained at the high power H2. In the third period CY11, the formation of the carbon-containing deposit DP is promoted. In the fourth period CY12, the high-frequency power LF can be maintained at the high power L2, and the high-frequency power HF can be maintained at the high power H2. In the fourth period CY12, the formation of the modified layer ML is promoted. In this way, the fourth period CY12, which is the period during which the high-frequency power LF is supplied, can be shorter than the first period CY1, which is the period during which the high-frequency power HF is supplied.

[0095] Fig.10 FIG. 1 is a timing chart showing another example of the temporal changes of the high frequency power and the bias power supplied to the plasma processing apparatus. Fig.10 The timing diagram is similar to that of Fig. 9 The timing diagram is the same as Fig.10 In the timing diagram of FIG. 1 , in the third period CY11, the high frequency power LF can be maintained at the medium power L3 (first bias power), and the high frequency power HF can be maintained at the high power H2. The medium power L3 can be a power between the low power L1 and the high power L2. In the third period CY11, the formation of the carbonaceous deposit DP is promoted. In the fourth period CY12, the high frequency power LF is maintained at the high power L2 (second bias power).

[0096] Figure 8 to Figure 10 The timing diagram can be changed as follows.

[0097] The high frequency power HF may be maintained at the high power H2 in a part of the first period CY1 , and maintained at a power different from the high power H2 and larger than the low power L1 in another part of the first period CY1 .

[0098] In the cycle CY, the proportion of the period during which the high-frequency power HF is maintained at the high power H2 (the duty ratio of the high-frequency power HF) can be changed. Similarly, in the cycle CY, the proportion of the period during which the high-frequency power LF is maintained at the high power L2 (the duty ratio of the high-frequency power LF) can be changed. The duty ratios of the high-frequency power HF and the high-frequency power LF can be adjusted so that almost all of the modified layer ML formed in the step ST3 is removed in the step ST4.

[0099] As time passes, at least one of the high power H2, the high power L2, the duty cycle of the high frequency power HF, the duty cycle of the high frequency power LF, the frequency of the cycle CY of the predetermined high frequency power HF, and the frequency of the cycle CY of the predetermined high frequency power LF may be changed. For example, as time passes, the high power L2 and the high power H2 may be increased, or the frequency of the cycle CY of the predetermined high frequency power LF may be decreased.

[0100] Fig.11 FIG. 1 is a cross-sectional view showing an etching device included in a plasma processing device according to an exemplary embodiment. The plasma processing device may include Fig.11 The etching apparatus 105 shown in FIG. 1 includes a chamber 140. No plasma is generated in the chamber 140. A substrate support portion 142 for supporting a substrate W is provided in the chamber 140. The etching apparatus 105 includes a gas supply portion 143 for supplying gas into the chamber 140 and an exhaust system 144 for reducing the pressure in the chamber 140.

[0101] The chamber 140 includes a chamber body 151 and a cover 152. The chamber body 151 includes a side wall 151a and a bottom 151b. The chamber body 151 has an opening at the top. The opening is closed by the cover 152. The side wall 151a and the bottom 151b are sealed by a sealing member.

[0102] The cover 152 includes a cover member 155 located outside and a shower head 156 embedded inside the cover member 155. The shower head 156 is provided so as to face the substrate support 142. The shower head 156 includes a main body 157 and a shower plate 158. The main body 157 includes, for example, a cylindrical side wall 157a and an upper wall 157b. The shower plate 158 is provided at the bottom of the main body 157. A space 159 is formed between the main body 157 and the shower plate 158.

[0103] The cover member 155 and the upper wall 157b are provided with a gas introduction path 161 penetrating into the space 159. The gas introduction path 161 is connected to a gas supply pipe 171 of the gas supply unit 143.

[0104] A plurality of gas ejection holes 162 are formed in the shower plate 158 . The gas introduced into the space 159 through the gas supply pipe 171 and the gas introduction path 161 is ejected from the gas ejection holes 162 into the space in the chamber 140 .

[0105] The side wall portion 151 a is provided with a gate 153 for transferring the substrate W between the space inside the chamber 140 and the space outside the chamber 140 . The gate 153 can be opened and closed by a gate valve 154 .

[0106] The substrate support portion 142 is connected to the bottom 151b of the chamber 140. A temperature regulator 165 for regulating the temperature of the substrate support portion 142 is provided in the substrate support portion 142. The temperature regulator 165 has, for example, a pipe for passing a temperature regulating medium such as water. The temperature of the substrate support portion 142 is regulated by heat exchange between the temperature regulating medium flowing in the pipe and the outer portion of the pipe. Thus, the temperature of the substrate W on the substrate support portion 142 is controlled.

[0107] The gas supply unit 143 includes a first gas supply source 175 for supplying a first gas and a second gas supply source 176 for supplying a second gas. The first gas is, for example, a modified gas MD. The second gas is, for example, a carbon-containing precursor PR. The first gas supply source 175 is connected to one end of a first gas supply pipe 172. The other end of the first gas supply pipe 172 is connected to a gas supply pipe 171. One end of a second gas supply pipe 173 is connected to the second gas supply source 176. The other end of the second gas supply pipe 173 is connected to the gas supply pipe 171. A flow controller 179 for opening and closing a flow path and controlling a flow rate is provided in the first gas supply pipe 172 and the second gas supply pipe 173, respectively.

[0108] Therefore, the first gas is supplied from the first gas supply source 175 to the shower head 156 via the first gas supply pipe 172. The second gas is supplied from the second gas supply source 176 to the shower head 156 via the second gas supply pipe 173. These gases are ejected from the gas ejection holes 162 of the shower head 156 toward the substrate W in the chamber 140.

[0109] The exhaust system 144 includes an exhaust pipe 182 connected to an exhaust port 181 formed at the bottom 151b of the chamber 140. The exhaust system 144 includes an automatic pressure control unit (APC: Automatic Pressure Control) 183 and a vacuum pump 184 provided in the exhaust pipe 182. The automatic pressure control unit 183 can control the pressure in the chamber 140. The vacuum pump 184 can exhaust the gas in the chamber 140 to the outside of the chamber 140.

[0110] Two capacitive pressure gauges 186a and 186b are provided on the side wall of the chamber 140 as pressure gauges for measuring the pressure in the chamber 140. The capacitive pressure gauges 186a and 186b penetrate the side wall of the chamber 140. The capacitive pressure gauge 186a can measure high pressure. The capacitive pressure gauge 186b can measure low pressure. A temperature sensor for detecting the temperature of the substrate W can be provided near the substrate W on the substrate support portion 142.

[0111] The gate 153 of the chamber 140 of the etching device 105 may be connected to a vacuum transfer module (VTM). Figure 2 The plasma processing chamber 10 of the plasma processing apparatus 1 may be connected to a vacuum transfer module. Thus, the substrate W can be transferred between the chamber 140 of the etching apparatus 105 and the plasma processing chamber 10 of the plasma processing apparatus 1 while maintaining a reduced pressure state.

[0112] In method MT, you can Figure 2 The plasma processing chamber 10 of the plasma processing apparatus 1 performs step ST3. Then, the substrate W can be transported by the vacuum transport module and Fig.11 Step ST4 is performed in the chamber 140 of the etching device 105.

[0113] Fig.12 FIG. 1 is a diagram showing a plasma processing apparatus according to an exemplary embodiment. Fig.12 The illustrated plasma processing apparatus PS can be used to carry out method MT.

[0114] The plasma processing apparatus PS includes platforms 3a to 3d, containers 4a to 4d, a loading module LM, an aligner AN, load lock modules LL1 and LL2, processing modules PM1 to PM6, a transport module TF, and a control unit 2. The number of platforms, the number of containers, and the number of load lock modules in the plasma processing apparatus PS may be any number greater than one. Furthermore, the number of processing modules in the plasma processing apparatus PS may be any number greater than two.

[0115] The platforms 3a to 3d are arranged along one edge of the loading module LM. The containers 4a to 4d are respectively mounted on the platforms 3a to 3d. The containers 4a to 4d are respectively, for example, containers called FOUP (Front Opening Unified Pod). The containers 4a to 4d are respectively configured to accommodate substrates W therein.

[0116] The loading module LM has a chamber. The pressure in the chamber of the loading module LM is set to atmospheric pressure. The loading module LM has a conveying device TU1. The conveying device TU1 is, for example, a multi-joint robot, and is controlled by the control unit 2. The conveying device TU1 is configured to be able to convey the substrate W through the chamber of the loading module LM. The conveying device TU1 is capable of conveying the substrate W between each of the containers 4a~4d and the aligner AN, between the aligner AN and each of the loading interlock modules LL1~LL2, and between each of the loading interlock modules LL1~LL2 and each of the containers 4a~4d. The aligner AN is connected to the loading module LM. The aligner AN is configured to be able to perform position adjustment (position calibration) of the substrate W.

[0117] The load lock module LL1 and the load lock module LL2 are respectively disposed between the loading module LM and the transfer module TF. The load lock module LL1 and the load lock module LL2 respectively provide a pre-decompression chamber.

[0118] The conveying module TF is connected to the loading interlock module LL1 and the loading interlock module LL2 via gate valves. The conveying module TF has a conveying chamber TC capable of reducing pressure. The conveying module TF has a conveying device TU2. The conveying device TU2 is, for example, a multi-joint robot, and is controlled by the control unit 2. The conveying device TU2 is configured to be able to convey the substrate W via the conveying chamber TC. The conveying device TU2 can convey the substrate W between each of the loading interlock modules LL1 to LL2 and each of the processing modules PM1 to PM6, and between any two of the processing modules PM1 to PM6.

[0119] The processing modules PM1 to PM6 are processing devices configured to perform dedicated substrate processing. One of the processing modules PM1 to PM6 can be Figure 2 Another processing module among the processing modules PM1-PM6 can be Fig.11 The chamber 140. One of the process modules PM1 to PM6 may include a film thickness meter as a monitoring device for monitoring the etching amount. Alternatively, the transport module TF may include a film thickness meter. In this case, the etching amount can be measured during the transport of the substrate W from one process module to another process module.

[0120] In the plasma processing apparatus PS, the control unit 2 is configured to be able to control each unit of the plasma processing apparatus PS. The plasma processing apparatus PS can transport the substrate W between the processing modules without exposing the substrate W to the atmosphere.

[0121] Various exemplary embodiments have been described above, but the present invention is not limited to the exemplary embodiments described above, and various additions, omissions, substitutions, and changes may be made. Furthermore, elements in different embodiments may be combined to form other embodiments.

[0122] It can be understood from the above description that various embodiments of the present invention are described in this specification for the purpose of illustration, and various changes can be made without departing from the scope and gist of the present invention. Therefore, the various embodiments disclosed in this specification are not intended to be limited, and the true scope and gist are represented by the attached technical solutions.

[0123] Explanation of symbols

[0124] 1…plasma processing device, 2…control unit, 10…plasma processing chamber, 11…substrate support unit, 12…plasma generating unit, 20…gas supply unit, MD…modified gas, ML…modified layer, PR…carbon-containing precursor, R1…first region, R1a…surface, R2…second region, W…substrate.

Claims

1. A plasma treatment method, It is characterized in that Include: (a) providing a substrate having a first region comprising a first material and a second region comprising a second material different from the first material; (b) supplying a modifying gas and a carbon-containing precursor for modifying the surface of the first region; (c) a step of modifying the surface of the first region to form a modified layer by using plasma generated from a mixed gas containing the modifying gas and the carbon-containing precursor by supplying a first high-frequency power; and (d) stopping supply of the first high-frequency power or supplying a second high-frequency power that is lower than the first high-frequency power to allow the modified layer to react with the carbon-containing precursor, thereby removing the modified layer.

2. The plasma treatment method according to claim 1, Features: The first region includes a metal-containing film, and the second region includes a mask.

3. The plasma treatment method according to claim 1 or 2, Features: The carbon-containing precursor is free of metal.

4. The plasma treatment method according to claim 3, Features: The carbon-containing precursor comprises at least one of an alcohol, a β-diketone, an amidine, an acetoamidine, and a β-ketodiimine.

5. The plasma treatment method according to claim 1 or 2, Features: During the period including the steps (c) and (d), the reforming gas and the carbon-containing precursor are continuously supplied.

6. The plasma treatment method according to claim 1 or 2, Features: The method further comprises the step (e) of repeatedly performing the steps (c) and (d).

7. The plasma treatment method according to claim 1 or 2, Features: In the (d), the substrate is heated.

8. The plasma treatment method according to claim 1 or 2, Features: The modifying gas includes at least one of a halogen-containing gas and an oxygen-containing gas.

9. The plasma treatment method according to claim 1 or 2, Features: The modifying gas includes at least one of a fluorine-containing gas and a chlorine-containing gas.

10. The plasma treatment method according to claim 1 or 2, Features: The modified gas comprises a gas selected from fluorocarbon gas, HF gas, NF 3 Gas, SF 6 Gas, chlorocarbon gas, Cl 2 Gas, NCl 3 Gas, SCl 6 Gas, O 2 Gas, CO gas and CO 2 at least one of the gases.

11. The plasma treatment method according to claim 1 or 2, Features: In the above (d), the supply of the first high-frequency power is stopped so that plasma is not generated.

12. The plasma treatment method according to claim 1 or 2, Features: In the step (c), a carbonaceous deposit is formed on the second region.

13. The plasma treatment method according to claim 1 or 2, Features: In the above (c), bias power is supplied to an electrode in a substrate supporter supporting the substrate.

14. The plasma processing method according to claim 13, Features: A period during which the bias power is supplied is shorter than a period during which the first high-frequency power is supplied.

15. The plasma processing method according to claim 13, Features: The bias power includes a first bias power and a second bias power greater than the first bias power.

16. A plasma treatment method, It is characterized in that Include: (a) providing a substrate having a metal-containing film and a mask on the metal-containing film; (b) supplying a modifying gas and a carbon-containing precursor for modifying the surface of the metal-containing film; (c) a step of modifying the surface of the metal-containing film to form a modified layer by using plasma generated from a mixed gas containing the modifying gas and the carbon-containing precursor by supplying a first high-frequency power; and (d) stopping the supply of the first high-frequency power to allow the modified layer to react with the carbon-containing precursor, thereby removing the modified layer.

17. A plasma treatment method, It is characterized in that Include: (a) a step of providing a substrate having a first region containing a metal and a second region containing an element other than the metal on a substrate support including an electrode; (b) a step of supplying a gas containing at least one of a halogen and oxygen and a carbon-containing precursor; and (c) removing the first region, The (c) comprises: (c1) a first period during which a first high frequency power is supplied; and (c2) A second period alternating with the first period, in which the first high-frequency power is not supplied or a second high-frequency power smaller than the first high-frequency power is supplied.

18. The plasma processing method according to claim 17, Features: The first high-frequency power and the second high-frequency power are high-frequency powers for plasma generation.

19. A plasma processing device, It is characterized in that have: Chamber; a substrate support for supporting a substrate within the chamber, the substrate having a first region comprising a first material and a second region comprising a second material different from the first material; a gas supply unit configured to supply a modifying gas and a carbon-containing precursor for modifying the surface of the first region into the chamber; a plasma generating unit configured to generate plasma from a mixed gas containing the reforming gas and the carbon-containing precursor by supplying a first high-frequency power in the chamber; and Control Department, The control unit is configured to control the gas supply unit and the plasma generation unit to perform the following steps: Modifying the surface of the first region by using the plasma to form a modified layer; and The first high-frequency power is stopped from being supplied or a second high-frequency power which is smaller than the first high-frequency power is supplied to allow the modified layer to react with the carbon-containing precursor, thereby removing the modified layer.

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