Chamber or component cleaning method, substrate processing method, and substrate processing apparatus

Abstract

A method for cleaning a chamber of a substrate processing apparatus or a component that is arranged within the chamber according to one exemplary embodiment of the present invention comprises: (a) a step in which a second metal-containing substance is formed from a first metal-containing substance that adheres to the chamber or the component with use of a first processing gas that contains a fluorine-containing gas within the chamber; and (b) a step in which the second metal-containing substance is removed with use of a second processing gas that contains a precursor within the chamber.

Description

[Technical Field]

[0001] SUMMARY Exemplary embodiments of the present disclosure relate to methods for cleaning a chamber or component, methods for processing substrates, and substrate processing apparatus. [Background technology]

[0002] Patent Document 1 discloses a method of etching a laminated film of an aluminum film and a titanium nitride film, and then cleaning the laminated film by converting a mixed gas of boron trichloride and chlorine into plasma. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-12515 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a cleaning method, a substrate processing method, and a substrate processing apparatus that can suppress damage to a chamber or components. [Means for solving the problem]

[0005] In one exemplary embodiment, a method for cleaning a chamber of a substrate processing apparatus or a component disposed within the chamber is provided, the method including: (a) forming a second metal-containing material from a first metal-containing material deposited on the chamber or the component within the chamber using a first process gas comprising a fluorine-containing gas, and (b) removing the second metal-containing material within the chamber using a second process gas comprising a precursor. [Effects of the Invention]

[0006] According to one exemplary embodiment, a cleaning method, a substrate processing method, and a substrate processing apparatus are provided that can reduce damage to the chamber or components. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a diagram schematically illustrating a substrate processing apparatus according to an exemplary embodiment. [Figure 2] FIG. 2 is a schematic diagram of a substrate processing apparatus according to an exemplary embodiment. [Figure 3] FIG. 3 is a diagram schematically illustrating a substrate processing apparatus according to another exemplary embodiment. [Figure 4] FIG. 4 is a diagram schematically illustrating a substrate processing apparatus according to another exemplary embodiment. [Figure 5] FIG. 5 is a partially enlarged cross-sectional view of an example substrate. [Figure 6] FIG. 6 is a flow chart of a cleaning method according to one exemplary embodiment. [Figure 7] FIG. 7 is a partially enlarged cross-sectional view of the example substrate processing apparatus in the process of etching a substrate. [Figure 8] FIG. 8 is a partially enlarged cross-sectional view of the example substrate processing apparatus in the step of forming a second metal-containing substance. [Figure 9] FIG. 9 is a partially enlarged cross-sectional view of the example substrate processing apparatus in the step of removing the second metal-containing material. [Figure 10] FIG. 10 is a partially enlarged cross-sectional view of the example substrate processing apparatus during a step of exposing the chamber or a component to plasma generated from the third process gas. DETAILED DESCRIPTION OF THE INVENTION

[0008] Various exemplary embodiments are described below.

[0009] In one exemplary embodiment, a method for cleaning a chamber of a substrate processing apparatus or a component disposed within the chamber includes: (a) forming a second metal-containing material from a first metal-containing material deposited on the chamber or the component using a first process gas comprising a fluorine-containing gas in the chamber; and (b) removing the second metal-containing material using a second process gas comprising a precursor in the chamber.

[0010] In the method of the above embodiment, in (a), a fluorine-containing gas reacts with a first metal-containing material to form a second metal-containing material. In addition, in (b), a precursor reacts with the second metal-containing material to remove the second metal-containing material. According to the method of the above embodiment, damage to the chamber or components due to cleaning can be suppressed compared to when metal-containing materials attached to the chamber or components are removed using chlorine gas.

[0011] The method may further include (c) exposing the chamber or the component to a third process gas or a plasma generated from the third process gas after (b), in which case residues present in the chamber or the component after removing the second metal-containing material can be removed.

[0012] The method may further include (d) etching a substrate placed in the chamber before (a). In this case, the chamber can be cleaned after etching the substrate.

[0013] The first pressure in the chamber in (d) may be lower than at least one of the second pressure in the chamber in (a) and the third pressure in the chamber in (b). In this case, the second pressure or the third pressure during cleaning is higher than the first pressure during etching, so that the supply amount of the fluorine-containing gas or precursor during cleaning can be increased, thereby increasing the cleaning rate.

[0014] The substrate may include a metal-containing film, in which case, even if the first metal-containing material adheres to the chamber or the component by etching the substrate, the first metal-containing material can be removed.

[0015] The method may further include (e) repeating (a) and (b) after (b), in which case more of the first metal-containing material can be removed.

[0016] In the step (a), the first processing gas may be used without generating plasma, which allows the first processing gas to reach a wider area in the chamber than when plasma is generated.

[0017] In the step (a), plasma generated from the first processing gas may be used.

[0018] In at least one of (a) and (b), the chamber or the component may be heated to promote the reaction between the first metal-containing material and the fluorine-containing gas or the reaction between the second metal-containing material and the precursor.

[0019] The precursor may include a metal-containing precursor, in which case the metal-containing precursor is capable of reacting with the second metal-containing material at low energy.

[0020] The metal-containing precursor may include a metal complex, in which case a ligand exchange reaction between the second metal-containing material and the metal complex produces another highly volatile metal complex.

[0021] The precursor may include a precursor that does not contain a metal, in which case metal residues are less likely to be generated by the reaction between the second metal-containing substance and the precursor.

[0022] In one exemplary embodiment, a substrate processing apparatus includes a chamber, a substrate support for supporting a substrate in the chamber, a gas supply unit configured to supply a first process gas containing hydrogen fluoride gas and a second process gas containing a precursor into the chamber, respectively, and a control unit, wherein the control unit is configured to control the gas supply unit to form a second metal-containing material from a first metal-containing material attached to the chamber or a component disposed in the chamber using the first process gas, and the control unit is configured to control the gas supply unit to remove the second metal-containing material from the chamber using the second process gas.

[0023] According to the substrate processing apparatus of the above embodiment, damage to the chamber or parts due to cleaning can be suppressed compared to when chlorine gas is used to remove metal-containing substances adhering to the chamber or parts.

[0024] The substrate processing apparatus may further include a heating device for heating the chamber or the component, in which case the heating promotes the reaction between the first metal-containing material and the fluorine-containing gas or the reaction between the second metal-containing material and the precursor.

[0025] Various exemplary embodiments will be described in detail below with reference to the drawings, in which the same or equivalent parts are designated by the same reference numerals.

[0026] 1 and 2 are diagrams schematically illustrating a substrate processing apparatus according to an exemplary embodiment, which is, for example, a plasma processing system.

[0027] In one embodiment, the plasma processing system includes a plasma processing device 1 and a controller 2. The plasma processing device 1 includes a plasma processing chamber 10, a substrate support 11, and a plasma generation unit 12. The plasma processing chamber 10 has a plasma processing space. The plasma processing chamber 10 also has at least one gas supply port for supplying at least one processing gas to the plasma processing space and at least one gas exhaust port for exhausting gas from the plasma processing space. The gas supply port is connected to a gas supply unit 20 (described later), and the gas exhaust port is connected to an exhaust system 40 (described later). The substrate support 11 is disposed in the plasma processing space and has a substrate support surface for supporting a substrate.

[0028] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be capacitively coupled plasma (CCP), inductively coupled plasma (ICP), electron-cyclotron-resonance plasma (ECR plasma), helicon wave plasma (HWP), or surface wave plasma (SWP). Various types of plasma generating units may be used, including alternating current (AC) plasma generating units and direct current (DC) plasma generating units. In one embodiment, the AC signal (AC power) used in the AC plasma generating unit has a frequency in the range of 100 kHz to 10 GHz. Therefore, the AC signal includes a radio frequency (RF) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 200 kHz to 150 MHz.

[0029] The controller 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform various processes described in this disclosure. The controller 2 may be configured to control each element of the plasma processing apparatus 1 to perform various processes described herein. In one embodiment, part or all of the controller 2 may be included in the plasma processing apparatus 1. The controller 2 may include, for example, a computer 2a. The computer 2a may include, for example, a processing unit (CPU: Central Processing Unit) 2a1, a storage unit 2a2, and a communication interface 2a3. The processing unit 2a1 may be configured to perform various control operations based on programs stored in the storage unit 2a2. 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).

[0030] An example of the configuration of a plasma processing system will be described below. 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 20, a power supply 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support 11 and a gas inlet. The gas inlet is configured to introduce at least one process gas into the plasma processing chamber 10. The gas inlet includes a showerhead 13. The substrate support 11 is disposed within the plasma processing chamber 10. The showerhead 13 is disposed above the substrate support 11. In one embodiment, the showerhead 13 forms at least a portion of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the showerhead 13, a sidewall 10a of the plasma processing chamber 10, and the substrate support 11. The plasma processing chamber 10 has at least one gas inlet for supplying at least one process gas to the plasma processing space 10s and at least one gas outlet for exhausting gas from the plasma processing space 10s. The sidewall 10a is grounded. The showerhead 13 and the substrate support 11 are electrically isolated from the plasma processing chamber 10 housing.

[0031] The substrate support 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central region (substrate support surface) 111a for supporting a substrate (wafer) W and an annular region (ring support surface) 111b for supporting the ring assembly 112. 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. In one embodiment, the main body 111 includes a base and an electrostatic chuck. The base includes a conductive member. The conductive member of the base functions as a lower electrode. The electrostatic chuck is disposed on the base. The upper surface of the electrostatic chuck has the substrate support surface 111a. The ring assembly 112 includes one or more annular members. At least one of the one or more annular members is an edge ring. Although not shown, the substrate support 11 may also include a temperature control module configured to adjust at least one of the electrostatic chuck, the ring assembly 112, and the substrate to a target temperature. The temperature control module may include a heater, a heat transfer medium, a flow path, or a combination thereof. A heat transfer fluid such as brine or gas flows through the flow path. The substrate support 11 may also include a heat transfer gas supply unit configured to supply a heat transfer gas between the back surface of the substrate W and the substrate support surface 111a.

[0032] The showerhead 13 is configured to introduce at least one processing gas from the gas supply unit 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and multiple gas inlets 13c. The processing gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the multiple gas inlets 13c. The showerhead 13 also includes a conductive member. The conductive member of the showerhead 13 functions as an upper electrode. In addition to the showerhead 13, the gas introduction unit may also include one or more side gas injectors (SGIs) attached to one or more openings formed in the sidewall 10a.

[0033] 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.

[0034] 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), such as a source RF signal and a bias RF signal, to the conductive members of the substrate support 11 and / or the conductive members of the showerhead 13. This causes plasma to be formed from at least one process gas supplied to the plasma processing space 10s. Therefore, the RF 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, supplying a bias RF signal to the conductive members of the substrate support 11 generates a bias potential on the substrate W, thereby attracting ion components in the formed plasma to the substrate W.

[0035] In one embodiment, the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b. The first RF generating unit 31a is coupled to the conductive members of the substrate support 11 and / or the conductive members of the showerhead 13 via at least one impedance matching circuit and is configured to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 13 MHz to 150 MHz. In one embodiment, the first RF generating unit 31a may be configured to generate multiple source RF signals having different frequencies. The generated one or more source RF signals are supplied to the conductive members of the substrate support 11 and / or the conductive members of the showerhead 13. The second RF generating unit 31b is coupled to the conductive members of the substrate support 11 via at least one impedance matching circuit and is configured to generate a bias RF signal (bias RF power). In one embodiment, the bias RF signal has a frequency lower than that of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 400 kHz to 13.56 MHz. In one embodiment, the second RF generator 31b may be configured to generate multiple bias RF signals having different frequencies. The generated bias RF signals are supplied to the conductive members of the substrate support 11. In various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0036] The power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generator 32a and a second DC generator 32b. In one embodiment, the first DC generator 32a is connected to a conductive member of the substrate support 11 and configured to generate a first DC signal. The generated first bias DC signal is applied to the conductive member of the substrate support 11. In one embodiment, the first DC signal may be applied to another electrode, such as an electrode in an electrostatic chuck. In one embodiment, the second DC generator 32b is connected to a conductive member of the showerhead 13 and configured to generate a second DC signal. The generated second DC signal is applied to the conductive member of the showerhead 13. In various embodiments, at least one of the first and second DC signals may be pulsed. The first and second DC generating units 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generating unit 32a may be provided instead of the second RF generating unit 31b.

[0037] The exhaust system 40 may be connected to, for example, a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure regulating valve regulates the pressure in the plasma processing space 10s. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0038] Fig. 3 is a diagram schematically illustrating a substrate processing apparatus according to another exemplary embodiment. The plasma processing apparatus 101 illustrated in Fig. 3 further includes a heating device 50 in addition to the configuration of the plasma processing apparatus 1 illustrated in Fig. 2. The heating device 50 can heat the plasma processing chamber 10 or a component (e.g., the substrate support 11) disposed in the plasma processing chamber 10.

[0039] The heating device 50 may include a microwave generator 51, a waveguide 52, and a quartz window 53. The microwave generator 51 is provided outside the plasma processing chamber 10, for example, above the shower head 13. The microwave generator 51 includes a magnetron and generates microwaves. The microwaves have a frequency of, for example, 2.45 GHz or 5.85 GHz. One end of the waveguide 52 is connected to the microwave generator 51. The other end of the waveguide 52 is connected to the quartz window 53. The quartz window 53 is provided in the shower head 13. The microwaves generated by the microwave generator 51 are irradiated toward the plasma processing chamber 10 or the substrate support 11 via the waveguide 52 and the quartz window 53. This heats the inner surface of the plasma processing chamber 10 or the surface of the substrate support 11. The direction of microwave irradiation can be adjusted by the positions or orientations of the waveguide 52 and the quartz window 53.

[0040] The heating device 50 may generate electromagnetic waves other than microwaves (for example, infrared rays) to heat the plasma processing chamber 10 or the substrate support 11. The heating device 50 may include an infrared lamp.

[0041] FIG. 4 is a diagram schematically illustrating a substrate processing apparatus according to another exemplary embodiment. A plasma processing apparatus 201 illustrated in FIG. 4 further includes a heating device 150 in addition to the configuration of the plasma processing apparatus 1 illustrated in FIG. 2. The heating device 150 can heat the plasma processing chamber 10. The heating device 150 may be a temperature control module embedded in the sidewall 10a of the plasma processing chamber 10. The temperature control module may be embedded in a portion of the plasma processing chamber 10 other than the sidewall 10a. The substrate support 11 may be heated by a temperature control module embedded in the substrate support 11. The temperature control module may include a heater, a heat transfer medium, a flow path, or a combination thereof.

[0042] 5 is a partially enlarged cross-sectional view of an example substrate. As shown in FIG. 5, in one embodiment, the substrate W includes an underlayer region UR and a metal-containing film MF. The metal-containing film MF is provided on the underlayer region UR. The underlayer region UR may be an underlayer film. The underlayer region UR may contain silicon.

[0043] The metal-containing film MF may contain at least one of oxygen and nitrogen. The metal-containing film MF may contain at least one of a metal oxide and a metal nitride. The metal-containing film MF may contain 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.

[0044] 6 is a flowchart of a cleaning method according to one exemplary embodiment. The cleaning method shown in FIG. 6 (hereinafter referred to as "method MT1") can be performed by the substrate processing apparatus of any of the above embodiments. Method MT1 may be a substrate processing method using the substrate processing apparatus of any of the above embodiments. Method MT1 may include steps ST1 to ST5. Steps ST1 to ST5 may be performed in order. Step ST1, step ST4, and step ST5 may not be performed.

[0045] Method MT1 will be described below with reference to FIGS. 6 to 10. When the plasma processing apparatus 1, 101, or 201 is used, method MT1 can be performed in the plasma processing apparatus 1, 101, or 201 by controlling each unit of the plasma processing apparatus 1, 101, or 201 by the control unit 2. Method MT1 can clean the plasma processing chamber 10 or a component (e.g., the substrate support 11) disposed in the plasma processing chamber 10. The following description will be given taking the cleaning of the plasma processing chamber 10 or the substrate support 11 as an example. Steps ST2 to ST5 of method MT1 may be performed with a cleaning substrate (dummy wafer) W1 disposed on the substrate support 11 instead of the substrate W. This can suppress damage to the substrate support 11 due to cleaning. Step ST1 may be performed with the substrate W disposed on the substrate support 11. After step ST1, the substrate W may be transported out of the plasma processing chamber 10. Thereafter, the cleaning substrate W1 may be transported into the plasma processing chamber 10. Thereafter, step ST3 may be performed.

[0046] (Process ST1) 7 is a partially enlarged cross-sectional view of an example substrate processing apparatus during a process of etching a substrate. In step ST1, a substrate W disposed in a plasma processing chamber 10 is etched. The substrate W may be etched using a plasma PL1. The plasma PL1 may be generated by a plasma generating unit 12 from a processing gas supplied from a gas supply unit 20 into the plasma processing chamber 10. The pressure within the plasma processing chamber 10 may be set to a first pressure P1 by an exhaust system 40.

[0047] After step ST1 is completed, a first metal-containing material MS1 may be deposited on the plasma processing chamber 10 or the substrate support 11 by etching. The first metal-containing material MS1 may coat the inner surface of the plasma processing chamber 10 and the surface of the substrate support 11. The first metal-containing material MS1 may contain the same metal as that contained in the metal-containing film MF. The first metal-containing material MS1 may contain 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. The first metal-containing material MS1 may contain at least one of oxygen and nitrogen. The first metal-containing material MS1 may contain at least one of a metal oxide and a metal nitride.

[0048] (Process ST2) 8 is a partially enlarged cross-sectional view of an example substrate processing apparatus during a step of forming a second metal-containing material. In step ST2, a first processing gas G1 containing a fluorine-containing gas is used in plasma processing chamber 10 to form a second metal-containing material MS2 from the first metal-containing material MS1 attached to plasma processing chamber 10 or substrate support 11. The second metal-containing material MS2 can coat the inner surface of plasma processing chamber 10 and the surface of substrate support 11. The first processing gas G1 is supplied into plasma processing chamber 10 from gas supply unit 20.

[0049] 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.

[0050] The second metal-containing material MS2 can be produced by reacting the first metal-containing material MS1 with a fluorine-containing gas. The second metal-containing material MS2 can contain the same metal as the first metal-containing material MS1 and fluorine. The second metal-containing material MS2 can be, for example, a metal fluoride. In one example, the first metal-containing material MS1 contains aluminum oxide, and the fluorine-containing gas contains hydrogen fluoride gas. In this case, the second metal-containing material MS2 contains aluminum fluoride.

[0051] In step ST2, the first process gas G1 may be used without generating plasma, or plasma generated from the first process gas G1 may be used. When plasma is not generated, the first process gas G1 may contain hydrogen fluoride gas.

[0052] In step ST2, the pressure in the plasma processing chamber 10 may be set to a second pressure P2 by the exhaust system 40. The second pressure P2 is greater than the first pressure P1 in step ST1. The second pressure P2 may be 100 mTorr (13 Pa) or greater.

[0053] In step ST2, the plasma processing chamber 10 or the substrate support 11 may be heated. The temperature of the plasma processing chamber 10 or the substrate support 11 may be 100°C or higher, 150°C or higher, or 200°C or higher. The temperature of the plasma processing chamber 10 or the substrate support 11 may be 450°C or lower. The heating may be performed by a plasma generated in the plasma processing chamber 10 or by the heating device 50, 150. The heating promotes the reaction between the first metal-containing material MS1 and the fluorine-containing gas.

[0054] A purge step may be performed after step ST2. In the purge step, a purge gas is supplied into the plasma processing chamber 10 and then exhausted. The purge gas is, for example, an inert gas such as nitrogen or argon.

[0055] (Process ST3) 9 is a partially enlarged cross-sectional view of an example substrate processing apparatus during a step of removing a second metal-containing material. In step ST3, the second metal-containing material MS2 is removed in the plasma processing chamber 10 using a second processing gas G2 containing a precursor. The second processing gas G2 is supplied into the plasma processing chamber 10 from the gas supply unit 20. In step ST3, the second processing gas G2 can be used without generating plasma.

[0056] The precursor may include a metal-containing precursor. The metal-containing precursor may include a metal complex. The metal complex may be a complex having a monodentate ligand or may be a chelate. The monodentate ligand may be at least one of an alkyl, a hydride, a carbonyl, a halide, an alkoxide, an alkylamide, and a silylamide. The chelate may be at least one of a β-diketonate, an amidinate, an acetamidinate, a β-diketiminate, a diaminoalkoxide, and a metallocene. The β-diketonate may be at least one of an acac (acetylacetonate), afac (hexafluoroacetylacetonate), tfac (trifluoroacetylacetonate), and ttmhd (tetramethylheptanedionate).

[0057] The metal contained in the metal-containing precursor can be at least one of Sn, Ge, Al, B, Ga, In, Zn, Ni, Pb, Si, Hf, Zr, and Ti.

[0058] The precursor may include a metal-free precursor. The metal-free precursor may include a carbon-containing precursor. The carbon-containing precursor may be at least one of an alcohol, a β-diketone, an amidine, an acetamidine, and a β-diketimine. The β-diketone may be at least one of acac (acetylacetone), hfac (hexafluoroacetylacetone), tfac (trifluoroacetylacetone), and tmhd (tetramethylheptanedione).

[0059] In step ST3, a volatile third metal-containing material MS3 can be generated by the reaction between the second metal-containing material MS2 and the precursor. This removes the second metal-containing material MS2. When the precursor includes a metal-containing precursor, the metal-containing precursor can react with the second metal-containing material with low energy. When the metal-containing precursor includes a metal complex, a ligand exchange reaction between the second metal-containing material MS2 and the metal complex generates another highly volatile metal complex. In one example, the second metal-containing material MS2 includes aluminum fluoride, and the metal-containing precursor includes tin(II) acetylacetonate (Sn(acac)2). When the precursor includes a metal-free precursor, metal residues are less likely to be generated by the reaction between the second metal-containing material and the precursor. When the metal-free precursor includes a carbon-containing precursor, residues containing carbon compounds are generated. The residues containing carbon compounds can be removed relatively easily.

[0060] In step ST3, the pressure in the plasma processing chamber 10 may be set to a third pressure P3 by the exhaust system 40. The third pressure P3 is greater than the first pressure P1 in step ST1. The third pressure P3 may be the same as or different from the second pressure P2 in step ST2.

[0061] In step ST3, similarly to step ST2, the plasma processing chamber 10 or the substrate support 11 may be heated, which promotes the reaction between the second metal-containing material MS2 and the precursor.

[0062] After step ST3, a purging step may be performed similarly to the purging step performed after step ST2.

[0063] (Process ST4) In step ST4, steps ST2 and ST3 are repeated. Steps ST2 and ST3 may be repeated multiple times. Step ST4 allows a larger amount of the first metal-containing material MS1 to be removed. Steps ST2 and ST3 are performed alternately. A purging step may be performed between steps ST2 and ST3.

[0064] (Process ST5) 10 is a partially enlarged cross-sectional view of an example substrate processing apparatus during a process of exposing a chamber or a component to plasma generated from a third process gas. In step ST5, the plasma processing chamber 10 or the substrate support 11 is exposed to plasma PL2 generated from the third process gas. The plasma PL2 may be generated by the plasma generation unit 12 from the third process gas supplied into the plasma processing chamber 10 from the gas supply unit 20. The plasma processing chamber 10 or the substrate support 11 may also be exposed to the third process gas without generating plasma.

[0065] The third process gas may include at least one of a fluorine-containing gas, an oxygen-containing gas, a hydrogen-containing gas, and a nitrogen-containing gas. The fluorine-containing gas may include at least one of 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 oxygen-containing gas may include at least one of oxygen gas, carbon monoxide gas, and carbon dioxide gas. The hydrogen-containing gas may include hydrogen gas. The nitrogen-containing gas may include nitrogen gas. When the precursor contained in the second process gas G2 includes Sn, the third process gas may include at least one of hydrogen gas, CH4 gas, and carbon monoxide gas. When the precursor contained in the second process gas G2 includes Si, Ge, or B, the third process gas may include a fluorine-containing gas. When the precursor contained in the second process gas G2 includes Pb, Ni, Al, Zn, Hf, or Zr, the third process gas may include at least one of CH4 gas and carbon monoxide gas. When the precursor contained in the second process gas G2 includes a precursor that does not contain a metal, the third process gas may include at least one of hydrogen gas and oxygen gas.

[0066] Step ST5 allows removal of residues (e.g., the first metal-containing material MS1, the second metal-containing material MS2, or other metal-containing materials) remaining in the plasma processing chamber 10 or the substrate support 11 after removing the second metal-containing material MS2.

[0067] According to the method MT1, damage to the plasma processing chamber 10 or the substrate support 11 caused by cleaning can be suppressed compared to when chlorine gas is used.

[0068] When the first pressure P1 in step ST1 is lower than the second pressure P2 in step ST2 or the third pressure P3 in step ST3, the supply amount of the fluorine-containing gas or precursor during cleaning can be increased, thereby increasing the cleaning speed.

[0069] When the first processing gas G1 is used without generating plasma in step ST2, the first processing gas G1 can reach a wider area in the plasma processing space 10s in the plasma processing chamber 10 than when plasma is generated. Furthermore, damage to the plasma processing chamber 10 or the substrate support 11 caused by the plasma can be suppressed.

[0070] Although various exemplary embodiments have been described above, the present invention is not limited to the above-described exemplary embodiments, and various additions, omissions, substitutions, and modifications may be made. Furthermore, elements in different embodiments may be combined to form other embodiments.

[0071] For example, the substrate processing apparatus does not have to include the plasma generating unit 12. In this case, plasma processing is not performed in the chamber of the substrate processing apparatus. Method MT1 can also be performed using such a substrate processing apparatus.

[0072] Various exemplary embodiments included in the present disclosure are described below in (Supplementary Note 1) to (Supplementary Note 20).

[0073] (Appendix 1) 1. A method for cleaning a chamber or a component disposed within a substrate processing apparatus, comprising: (a) forming a second metal-containing material from a first metal-containing material deposited on the chamber or the component using a first process gas comprising a fluorine-containing gas in the chamber; (b) removing the second metal-containing material in the chamber using a second process gas comprising a precursor; A method comprising:

[0074] (Appendix 2) 2. The method of claim 1, further comprising the step of (c) after (b), exposing the chamber or the component to a third process gas or a plasma generated from the third process gas.

[0075] (Appendix 3) 3. The method of claim 1 or 2, further comprising (d) prior to (a), etching a substrate disposed in the chamber.

[0076] (Appendix 4) 4. The method of claim 3, wherein the first pressure in the chamber in (d) is less than at least one of the second pressure in the chamber in (a) and the third pressure in the chamber in (b).

[0077] (Appendix 5) 5. The method of claim 3 or 4, wherein the substrate comprises a metal-containing film.

[0078] (Appendix 6) (e) The method according to any one of appendices 1 to 5, further comprising the step of repeating (a) and (b) after (b).

[0079] (Appendix 7) 7. The method according to any one of claims 1 to 6, wherein in (a), the first process gas is used without generating plasma.

[0080] (Appendix 8) 7. The method according to any one of claims 1 to 6, wherein in (a), plasma generated from the first processing gas is used.

[0081] (Appendix 9) 9. The method according to any one of claims 1 to 8, wherein in at least one of (a) and (b), the chamber or the part is heated.

[0082] (Appendix 10) 10. The method of any one of claims 1 to 9, wherein the precursor comprises a metal-containing precursor.

[0083] (Appendix 11) 11. The method of claim 10, wherein the metal-containing precursor comprises a metal complex.

[0084] (Appendix 12) 12. The method of claim 11, wherein the metal complex is a complex having at least one monodentate ligand selected from the group consisting of alkyl, hydride, carbonyl, halide, alkoxide, alkylamide, and silylamide, or at least one chelate selected from the group consisting of β-diketonate, amidinate, acetamidinate, β-diketiminate, diaminoalkoxide, and metallocene.

[0085] (Appendix 13) 13. The method of any one of claims 1 to 12, wherein the precursor comprises a metal-free precursor.

[0086] (Appendix 14) 14. The method of claim 13, wherein the metal-free precursor is at least one β-diketone selected from the group consisting of acac (acetylacetone), hfac (hexafluoroacetylacetone), tfac (trifluoroacetylacetone), and tmhd (tetramethylheptanedione).

[0087] (Appendix 15) a chamber; a gas supply configured to supply a first process gas containing a fluorine-containing gas and a second process gas containing a metal-containing precursor or a carbon-containing precursor into the chamber; A substrate processing method using a substrate processing apparatus comprising: The substrate processing method includes: (a) etching a substrate having an underlayer and a metal-containing film on the underlayer in the chamber, wherein the etching causes a first metal-containing material to adhere to the chamber or a component disposed in the chamber, the first metal-containing material including the metal contained in the metal-containing film; (b) forming a second metal-containing material from the first metal-containing material in the chamber using the first process gas; (c) removing the second metal-containing material in the chamber using the second process gas; Including, the metal-containing film contains at least one selected from the group consisting of Al, Hf, Zr, Fe, Ni, Co, Mn, Mg, Rh, Ru, Cr, Si, T, Ga, In, Zn, Pb, Ge, Ta, Cu, W, Mo, Pt, Cd, and Sn; the fluorine-containing gas includes at least one selected from the group consisting of a hydrogen fluoride gas, a fluorocarbon gas, a nitrogen-containing gas, and a sulfur-containing gas; the metal-containing precursor is a complex or chelate having a monodentate ligand and containing at least one metal selected from the group consisting of Sn, Ge, Al, B, Ga, In, Zn, Ni, Pb, Si, Hf, Zr, and Ti; the carbon-containing precursor is at least one selected from the group consisting of alcohols, β-diketones, amidines, acetamidines, and β-diketimines; Substrate processing method.

[0088] (Appendix 16) a chamber; a substrate support for supporting a substrate within the chamber; a gas supply unit configured to supply a first process gas containing hydrogen fluoride gas and a second process gas containing a precursor into the chamber; A control unit; Equipped with the control unit is configured to control the gas supply unit to use the first process gas in the chamber to form a second metal-containing material from a first metal-containing material attached to the chamber or a component disposed in the chamber; The substrate processing apparatus, wherein the controller is configured to control the gas supply unit to remove the second metal-containing material using the second process gas in the chamber.

[0089] (Appendix 17) 17. The substrate processing apparatus of claim 16, further comprising a heating device for heating the chamber or the component.

[0090] (Appendix 18) 18. The substrate processing apparatus according to claim 17, wherein the heating device is a device that heats the chamber or the component by electromagnetic waves.

[0091] (Appendix 19) 19. The substrate processing apparatus according to claim 18, wherein the heating device includes a microwave generating unit.

[0092] (Appendix 20) 18. The substrate processing apparatus of claim 17, wherein the heating device is a temperature control module disposed in a sidewall of the chamber or in the substrate support.

[0093] From the foregoing, it will be understood that various embodiments of the present disclosure have been described herein for purposes of illustration, and that various modifications may be made without departing from the scope and spirit of the present disclosure. Accordingly, the various embodiments disclosed herein are not intended to be limiting, with the true scope and spirit being indicated by the appended claims. [Explanation of symbols]

[0094] 2...controller, 10...plasma processing chamber, 11...substrate support, 20...gas supply unit, G1...first processing gas, G2...second processing gas, MS1...first metal-containing substance, MS2...second metal-containing substance, W...substrate.

Claims

1. 1. A method for cleaning a chamber or a component disposed within a substrate processing apparatus, comprising: (a) forming a second metal-containing material from a first metal-containing material deposited on the chamber or the component using a first process gas comprising a fluorine-containing gas in the chamber; (b) removing the second metal-containing material in the chamber using a second process gas comprising a precursor; Including, In the step (a), the first processing gas is used without generating plasma; The method, wherein the precursor comprises a metal-containing precursor.

2. 10. The method of claim 1, further comprising: (c) after (b), exposing the chamber or the component to a third process gas or a plasma generated from the third process gas.

3. 3. The method of claim 2, wherein the third process gas comprises at least one of a fluorine-containing gas, an oxygen-containing gas, a hydrogen-containing gas, and a nitrogen-containing gas.

4. The method of claim 2 , wherein the third process gas comprises at least one of a fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas.

5. A method for cleaning a chamber of a substrate processing apparatus or a component disposed within said chamber, comprising: (a) forming a second metal-containing material from a first metal-containing material deposited on the chamber or the component using a first process gas comprising a fluorine-containing gas in the chamber; (b) removing the second metal-containing material in the chamber using a second process gas comprising a precursor; (c) after (b), exposing the chamber or the component to a third process gas or a plasma generated from the third process gas; Including, In the step (a), the first processing gas is used without generating plasma; When the precursor contains Sn, the third process gas contains at least one of hydrogen gas, CH 4 gas, and carbon monoxide gas; When the precursor comprises Si, Ge, or B, the third process gas comprises a fluorine-containing gas; When the precursor includes Pb, Ni, Al, Zn, Hf, or Zr, the third process gas includes at least one of CH 4 gas and carbon monoxide gas; When the precursor comprises a metal-free precursor, the third process gas comprises at least one of hydrogen gas and oxygen gas.

6. The method of any one of claims 1 to 5, further comprising the step of: (d) prior to (a), etching a substrate disposed in the chamber.

7. 7. The method of claim 6, wherein the first pressure in the chamber in (d) is less than at least one of the second pressure in the chamber in (a) and the third pressure in the chamber in (b).

8. The method of claim 6 , wherein the substrate comprises a metal-containing film.

9. The method of any one of claims 1 to 5, further comprising the step of: (e) after (b), repeating (a) and (b).

10. The method according to any one of claims 1 to 5, wherein in at least one of (a) and (b), the chamber or the part is heated.

11. The method of claim 5 , wherein the precursor comprises a metal-containing precursor.

12. The method of any one of claims 1 to 4, 11, wherein the metal-containing precursor comprises a metal complex.

13. 13. The method of claim 12, wherein the metal complex is a complex having at least one monodentate ligand selected from the group consisting of alkyl, hydride, carbonyl, halide, alkoxide, alkylamide, and silylamide, or at least one chelate selected from the group consisting of β-diketonate, amidinate, acetamidinate, β-diketiminate, diaminoalkoxide, and metallocene.

14. The method of any one of claims 1 to 5, wherein the precursor comprises a metal-free precursor.

15. 15. The method of claim 14, wherein the metal-free precursor is at least one β-diketone selected from the group consisting of acac (acetylacetone), hfac (hexafluoroacetylacetone), tfac (trifluoroacetylacetone), and tmhd (tetramethylheptanedione).

16. When the precursor contains Sn, the third process gas is hydrogen gas, CH ４ gas and carbon monoxide gas; When the precursor comprises Si, Ge, or B, the third process gas comprises a fluorine-containing gas; When the precursor includes Pb, Ni, Al, Zn, Hf, or Zr, the third process gas is CH ４ gas and carbon monoxide gas; 3. The method of claim 2, wherein when the precursor comprises a metal-free precursor, the third process gas comprises at least one of hydrogen gas and oxygen gas.

17. a chamber; a gas supply configured to supply a first process gas including a fluorine-containing gas and a second process gas including a metal-containing precursor into the chamber; A substrate processing method using a substrate processing apparatus comprising: The substrate processing method includes: (a) etching a substrate having an underlayer and a metal-containing film on the underlayer in the chamber, wherein the etching causes a first metal-containing material to adhere to the chamber or a component disposed in the chamber, the first metal-containing material including the metal contained in the metal-containing film; (b) forming a second metal-containing material from the first metal-containing material in the chamber using the first process gas; (c) removing the second metal-containing material in the chamber using the second process gas; Including, the metal-containing film contains at least one selected from the group consisting 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; the fluorine-containing gas includes at least one selected from the group consisting of a hydrogen fluoride gas, a fluorocarbon gas, a nitrogen-containing gas, and a sulfur-containing gas; the metal-containing precursor is a complex or chelate having a monodentate ligand and containing at least one metal selected from the group consisting of Sn, Ge, Al, B, Ga, In, Zn, Ni, Pb, Si, Hf, Zr, and Ti; In the step (b), the first processing gas is used without generating plasma. Substrate processing method.

18. a chamber; a substrate support for supporting a substrate within the chamber; a gas supply unit configured to supply into the chamber a first process gas containing hydrogen fluoride gas and a second process gas containing a precursor including a metal-containing precursor; A control unit; Equipped with the controller is configured to control the gas supply unit to form, in the chamber, a second metal-containing material from a first metal-containing material attached to the chamber or a component disposed in the chamber using the first process gas without generating a plasma; The substrate processing apparatus, wherein the controller is configured to control the gas supply unit to remove the second metal-containing material using the second process gas in the chamber.

19. A chamber; a substrate support for supporting a substrate within the chamber; a gas supply unit configured to supply a first process gas containing hydrogen fluoride gas, a second process gas containing a precursor, and a third process gas into the chamber; A control unit; Equipped with the controller is configured to control the gas supply unit to form, in the chamber, a second metal-containing material from a first metal-containing material attached to the chamber or a component disposed in the chamber using the first process gas without generating a plasma; the controller is configured to control the gas supply unit to remove the second metal-containing material using the second process gas in the chamber; the controller is configured to control the gas supply unit to remove the second metal-containing material using the second process gas in the chamber; the controller is configured to control the gas supply unit to expose the chamber or the component to the third process gas or plasma generated from the third process gas after removing the second metal-containing material; When the precursor contains Sn, the third process gas contains at least one of hydrogen gas, CH 4 gas, and carbon monoxide gas; When the precursor comprises Si, Ge, or B, the third process gas comprises a fluorine-containing gas; When the precursor includes Pb, Ni, Al, Zn, Hf, or Zr, the third process gas includes at least one of CH 4 gas and carbon monoxide gas; When the precursor includes a metal-free precursor, the third process gas includes at least one of hydrogen gas and oxygen gas. Substrate processing equipment.

20. The substrate processing apparatus according to claim 18 or 19, further comprising a heating device for heating the chamber or the part.

21. The substrate processing apparatus according to claim 20 , wherein the heating device is a device that heats the chamber or the component by electromagnetic waves.

22. The substrate processing apparatus of claim 21 , wherein the heating device comprises a microwave generator.

23. The substrate processing apparatus of claim 20 , wherein the heating device is a temperature control module disposed in a sidewall of the chamber or in the substrate support.

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