Substrate processing method and plasma processing apparatus

Abstract

To provide a substrate processing method and a plasma processing apparatus that can remove a metal-containing layer.SOLUTION: In one exemplary embodiment, a substrate processing method includes: (a) a step of providing a substrate, the substrate comprising a first area including first material containing silicon and a second area including second material different from the first material; (b) a step of etching the second area, while forming a metal-containing layer on the first area with plasma generated from processing gas containing halogen and metal; and (c) a step of removing the metal-containing layer with a base.SELECTED DRAWING: Figure 3

Description

[Technical Field]

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

[0002] Patent Document 1 discloses a method for etching an insulating film using plasma. In this method, etching is performed while forming a conductive layer on the surface of the insulating film. The etching uses plasma generated from a mixed gas of WF6 and C4F8. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 9-50984 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a substrate processing method and a plasma processing apparatus capable of removing a metal-containing layer. [Means for solving the problem]

[0005] In one exemplary embodiment, a substrate processing method includes: (a) providing a substrate, the substrate having a first region including a first material including silicon and a second region including a second material different from the first material; (b) etching the second region using plasma generated from a process gas including a halogen and a metal while forming a metal-containing layer on the first region; and (c) removing the metal-containing layer using a base. [Effects of the Invention]

[0006] According to one exemplary embodiment, a substrate processing method and plasma processing apparatus capable of removing a metal-containing layer are provided. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a diagram schematically illustrating a plasma processing apparatus according to an exemplary embodiment. [Figure 2] FIG. 2 is a diagram schematically illustrating a plasma processing apparatus according to an exemplary embodiment. [Figure 3] FIG. 3 is a flowchart of a substrate processing method according to one exemplary embodiment. [Figure 4] FIG. 4 is a cross-sectional view of an example substrate to which the method of FIG. 3 can be applied. [Figure 5] FIG. 5 is a cross-sectional view illustrating a step of a substrate processing method according to an exemplary embodiment. [Figure 6] FIG. 6 is a cross-sectional view illustrating a step of a substrate processing method according to an exemplary embodiment. [Figure 7] FIG. 7 is a flowchart of a substrate processing method according to an exemplary embodiment. [Figure 8] FIG. 8 is an example of a timing chart showing the time variation of the bias RF power applied to the electrode in the main body and the source RF power applied to the counter electrode. [Figure 9] FIG. 9 is a diagram schematically illustrating a substrate processing apparatus according to an exemplary embodiment. DETAILED DESCRIPTION OF THE INVENTION

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

[0009] FIG. 1 is a diagram illustrating an exemplary configuration 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 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.

[0010] 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 100 kHz to 150 MHz.

[0011] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform various processes described in this disclosure. The control unit 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 control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 may include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. The control unit 2 may be implemented by, for example, a computer 2a. The processing unit 2a1 may be configured to read a program from the storage unit 2a2 and execute the read program to perform various control operations. The program may be stored in the storage unit 2a2 in advance or may be acquired via a medium when needed. The acquired program is stored in the storage unit 2a2 and read from the storage unit 2a2 by the processing unit 2a1 for execution. The medium may be various storage media readable by the computer 2a or a communication line connected to the communication interface 2a3. The processing unit 2a1 may be a CPU (Central Processing Unit). 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).

[0012] The following describes a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1. Fig. 2 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0013] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply 20, a power supply 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support 11 and a gas inlet. The gas inlet is configured to introduce at least one process gas into the plasma processing chamber 10. The gas inlet includes a showerhead 13. The substrate support 11 is disposed within the plasma processing chamber 10. The showerhead 13 is disposed above the substrate support 11. In one embodiment, the showerhead 13 forms at least a portion of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the showerhead 13, a sidewall 10a of the plasma processing chamber 10, and the substrate support 11. The plasma processing chamber 10 is grounded. The showerhead 13 and the substrate support 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0014] The substrate support 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central region 111a for supporting a substrate W and an annular region 111b for supporting the ring assembly 112. A wafer is an example of a substrate W. The annular region 111b of the main body 111 surrounds the central region 111a of the main body 111 in a plan view. The substrate W is disposed on the central region 111a of the main body 111, and the ring assembly 112 is disposed on the annular region 111b of the main body 111 so as to surround the substrate W on the central region 111a of the main body 111. Therefore, the central region 111a is also called a substrate support surface for supporting the substrate W, and the annular region 111b is also called a ring support surface for supporting the ring assembly 112.

[0015] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive member. The conductive member of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is disposed on the base 1110. The electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within the ceramic member 1111a. The ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that the annular region 111b may also be provided by another member surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member. In this case, the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating member, or may be disposed on both the electrostatic chuck 1111 and the annular insulating member. Furthermore, at least one RF / DC electrode coupled to an RF power supply 31 and / or a DC power supply 32, which will be described later, may be disposed within the ceramic member 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or a DC signal, which will be described later, is supplied to the at least one RF / DC electrode, the RF / DC electrode is also called a bias electrode. Note that the conductive member of the base 1110 and the at least one RF / DC electrode may function as multiple lower electrodes. Alternatively, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support 11 includes at least one lower electrode.

[0016] The ring assembly 112 includes one or more annular members. In one embodiment, the one or more annular members include one or more edge rings and at least one cover ring. The edge rings are formed of a conductive or insulating material, and the cover rings are formed of an insulating material.

[0017] The substrate support 11 may also include a temperature adjustment module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature adjustment module may include a heater, a heat transfer medium, a flow passage 1110a, or a combination thereof. A heat transfer fluid such as brine or a gas flows through the flow passage 1110a. In one embodiment, the flow passage 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111. The substrate support 11 may also include a heat transfer gas supply configured to supply a heat transfer gas to a gap between the backside of the substrate W and the central region 111a.

[0018] 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 at least one 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.

[0019] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one process gas from a corresponding gas source 21 to the showerhead 13 via a corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Additionally, the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of the at least one process gas.

[0020] The power supply 30 includes an RF power supply 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The RF power supply 31 is configured to supply at least one RF signal (RF power) to at least one lower electrode and / or at least one upper electrode. This generates a plasma from at least one processing gas supplied to the plasma processing space 10s. Therefore, the RF power supply 31 can function as at least a part of the plasma generation unit 12. Furthermore, by supplying a bias RF signal to the at least one lower electrode, a bias potential is generated on the substrate W, and ion components in the formed plasma can be attracted to the substrate W.

[0021] In one embodiment, the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b. The first RF generating unit 31a is coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit and is configured to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generating unit 31a may be configured to generate multiple source RF signals having different frequencies. The generated one or more source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0022] The second RF generating unit 31b is coupled to at least one lower electrode via at least one impedance matching circuit and configured to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF generating unit 31b may be configured to generate multiple bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. In various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0023] 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 at least one lower electrode and configured to generate a first DC signal. The generated first DC signal is applied to the at least one lower electrode. In one embodiment, the second DC generator 32b is connected to at least one upper electrode and configured to generate a second DC signal. The generated second DC signal is applied to the at least one upper electrode.

[0024] In various embodiments, the first and second DC signals may be pulsed. In this case, a sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulses may have a rectangular, trapezoidal, triangular, or combination thereof. In one embodiment, a waveform generator for generating a sequence of voltage pulses from the DC signal is connected between the first DC generator 32a and at least one lower electrode. Thus, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. When the second DC generator 32b and the waveform generator constitute a voltage pulse generator, the voltage pulse generator is connected to at least one upper electrode. The voltage pulses may have either positive or negative polarity. Furthermore, the sequence of voltage pulses may include one or more positive voltage pulses and one or more negative voltage pulses within one period. The first and second DC generating units 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generating unit 32a may be provided instead of the second RF generating unit 31b.

[0025] 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.

[0026] 3 is a flowchart of a substrate processing method according to one exemplary embodiment. The substrate processing method MT1 (hereinafter referred to as "method MT1") shown in FIG. 3 can be performed by the plasma processing apparatus 1 according to the above embodiment. The method MT1 can be applied to a substrate W.

[0027] 4 is a cross-sectional view of an example substrate to which the method of FIG. 3 can be applied. As shown in FIG. 4, in one embodiment, the substrate W includes a first region R1 and a second region R2. The first region R1 may have at least one recess R1a. The first region R1 may have multiple recesses R1a. Each recess R1a may be a recess for forming a contact hole. The second region R2 may be embedded in the recess R1a. The second region R2 may be provided to cover the first region R1.

[0028] The first region R1 includes a first material including silicon. The first region R1 may be a silicon-containing region. The first region R1 may further include nitrogen. The first region R1 may be a silicon nitride (SiN x The first region R1 may include a silicon nitride (SiN x The first portion may include a first portion including silicon carbide (SiC), and a second portion including silicon carbide (SiC). In this case, the first portion has a recess R1a.

[0029] The second region R2 includes a second material different from the first material of the first region R1. The second region R2 may include silicon and oxygen. The second region R2 may include silicon oxide (SiO x The second region R2 may include a recess R2a. The recess R2a has a width greater than that of the recess R1a. The second region R2 may be a region formed by, for example, CVD or the like, or may be a region obtained by oxidizing silicon. The second region R2 may have a recess R2a. The recess R2a has a width greater than that of the recess R1a.

[0030] The substrate W may include an underlying region UR and at least one raised region RA provided on the underlying region UR. The underlying region UR and the at least one raised region RA are covered by a first region R1. The underlying region UR may include silicon. A plurality of raised regions RA are located on the underlying region UR. Recesses R1a of the first region R1 are located between the plurality of raised regions RA. Each raised region RA may form a gate region of a transistor.

[0031] The substrate W may include a mask MK. The mask MK is provided on the second region R2. The mask MK may include metal or silicon. The mask MK may have an opening OP. The opening OP corresponds to the recess R2a in the second region R2.

[0032] Method MT1 will be described below with reference to FIGS. 3 to 6, taking as an example a case where method MT1 is applied to a substrate W using the plasma processing apparatus 1 of the above embodiment. Each of FIGS. 4 to 6 is a cross-sectional view showing one step of a substrate processing method according to one exemplary embodiment. When the plasma processing apparatus 1 is used, method MT1 can be performed in the plasma processing apparatus 1 by controlling each part of the plasma processing apparatus 1 with a control unit 2. In method MT1, a substrate W on a substrate support 11 arranged in a plasma processing chamber 10 is processed, as shown in FIG. 2.

[0033] As shown in Figure 3, method MT1 may include steps ST1 to ST5. Steps ST1 to ST5 may be performed in order. Step ST4 may be performed in the same chamber as step ST2. Method MT1 may not include at least one of step ST2, step ST3, and step ST4. Step ST2 may be included in step ST1.

[0034] (Process ST1) In step ST1, a substrate W shown in FIG. 4 is provided. The substrate W may be supported by a substrate support 11 in a plasma processing chamber 10. The substrate W may have the shape shown in FIG. 4 as a result of plasma etching, or may have the shape shown in FIG. 4 from the beginning when provided to the plasma processing chamber 10. In step ST1, the second region R2 may be provided to cover the first region R1. In step ST1, the upper surfaces of the first region R1 and the second region R2 may be exposed. That is, in step ST1, the upper surfaces of the silicon nitride and the silicon oxide may be exposed.

[0035] (Process ST2) In step ST2, as shown in FIG. 5, plasma PL1 generated from a process gas may be used to etch the second region R2 while forming a metal-containing layer DP1 on the first region R1. Contact holes HL corresponding to the recesses R1a may be formed by etching. That is, step ST2 may be performed as a self-aligned contact (SAC) etching process. The metal-containing layer DP1 may contain at least one of molybdenum, tungsten, titanium, niobium, rhenium, osmium, ruthenium, platinum, germanium, or tantalum. The metal-containing layer DP1 may contain at least one of halogen, carbon, and nitrogen. The halogen may include at least one of fluorine, chlorine, bromine, or iodine. A carbon-containing layer DP2 may be formed on the metal-containing layer DP1 by plasma PL1. The carbon-containing layer DP2 may contain at least one of halogen and nitrogen. The halogen may include at least one of fluorine, chlorine, bromine, or iodine. The metal-containing layer DP1 and the carbon-containing layer DP2 may be formed on the shoulder portion SH of the recess R1a of the first region R1, or may be formed on the bottom of the recess R1a. In step ST2, the second region R2 may be etched to expose the first region R1. In step ST2, the first region R1 may also be etched. In particular, the shoulder portion SH of the recess R1a of the first region R1 may be etched.

[0036] The process gas in step ST2 may contain a halogen and a metal. The halogen may include at least one of fluorine, chlorine, bromine, and iodine. The metal may be at least one of molybdenum, tungsten, titanium, niobium, rhenium, osmium, ruthenium, platinum, germanium, and tantalum. The process gas in step ST2 may further contain carbon. The process gas in step ST2 may include a metal halide gas. The metal halide gas may include fluorine. The metal halide gas may include at least one selected from the group consisting of WF6 gas, MoF6 gas, WCl6 gas, TiCl4 gas, NbF5 gas, ReF6 gas, ReF7 gas, OsF6 gas, RuF5, RuF6, PtF6 gas, GeF4, and TaF5. The process gas in step ST2 may include a tungsten-containing gas containing fluorine. An example of the tungsten-containing gas containing fluorine includes tungsten hexafluoride (WF6) gas. The tungsten-containing gas contained in the processing gas in step ST2 may include a tungsten halide gas. The tungsten halide gas may include at least one of tungsten hexafluoride (WF6) gas, tungsten hexabromide (WBr6) gas, tungsten hexachloride (WCl6) gas, and WF5Cl gas. The tungsten-containing gas contained in the processing gas in step ST2 may include tungsten hexacarbonyl (W(CO)6) gas. The processing gas in step ST2 may further include a fluorine-containing gas containing carbon. The processing gas in step ST2 may include at least one of a fluorocarbon gas and a hydrofluorocarbon gas. Fluorocarbon (C x F y Examples of gases include hydrofluorocarbons (C ) including CF , C , C , C , C , and C . x H y F z Examples of the gas include CH2F2 gas, CHF3 gas, and CH3F gas. The processing gas in step ST2 may further include an oxygen-containing gas. Examples of the oxygen-containing gas include oxygen gas. The processing gas in step ST2 may further include a noble gas.

[0037] In one example, the process gas may contain a metal immediately before the first region R1 is exposed. A mask MK is used in the etching. The etching may be performed as follows: First, the gas supply unit 20 supplies a process gas into the plasma processing chamber 10. Next, the plasma generation unit 12 generates plasma PL1 from the process gas in the plasma processing chamber 10. The control unit 2 controls the gas supply unit 20 and the plasma generation unit 12 so that the second region R2 is etched to expose the first region R1. In step ST2, bias power may or may not be applied to the electrode in the main body 111 of the substrate support 11. In particular, bias power may not be applied immediately before or after the first region R1 is exposed. As a result, deposits are more likely to be formed, and etching of the shoulder portion SH of the recess R1a is suppressed.

[0038] (Process ST3) In step ST3, the substrate W may be exposed to the atmosphere. The substrate W may be taken out of the plasma processing chamber 10. The atmosphere contains nitrogen gas and oxygen gas. The atmosphere may further contain water or water vapor (H2O). The carbon-containing layer DP2 may be modified by the gases in the atmosphere.

[0039] (Process ST4) In step ST4, the substrate W may be exposed to plasma generated from an inert gas. The inert gas may include a nitrogen-containing gas. An example of the nitrogen-containing gas includes nitrogen gas. Step ST4 may be performed in the plasma processing chamber 10. The carbon-containing layer DP2 may be modified by the plasma generated from the inert gas.

[0040] (Process ST5) In step ST5, as shown in FIG. 6, the metal-containing layer DP1 is removed using a base. The metal-containing layer DP1 may be partially or entirely removed. The carbon-containing layer DP2 may also be removed. The carbon-containing layer DP2 may also be partially or entirely removed. Step ST5 may be performed in a plasma processing chamber 10 different from the chamber in which step ST2 or step ST4 is performed.

[0041] The pH of the base is greater than 7. The pH of the base may be 11 or less. The base may be a gas or a liquid. The base may include at least one of ammonia, sodium carbonate, and sodium bicarbonate. The base may include an aqueous ammonium solution. The ammonia concentration of the aqueous ammonium solution may be 500 ppm or less, or may be 200 ppm or less.

[0042] After step ST5, the first region R1 located at the bottom of the recess R1a may be etched with plasma, and the etching may be performed so as to expose the underlying region UR.

[0043] According to the method MT1, the metal-containing layer DP1 can be removed by reacting it with a base.

[0044] When the method MT1 includes at least one of step ST3 and step ST4, the carbon-containing layer DP2 can be removed in step ST5.

[0045] Various experiments performed to evaluate Method MT1 are described below, but the experiments described below are not intended to limit the present disclosure.

[0046] (First experiment) In the first experiment, a substrate W shown in FIG. 4 was prepared. The substrate W was made of silicon nitride (SiN x a first region R1 including a silicon oxide (SiO x ) and a second region R2 including the first region R1. Thereafter, the plasma processing apparatus 1 was used to perform steps ST2 to ST5 on the substrate W.

[0047] In step ST2, plasma PL1 was generated from a processing gas containing tungsten hexafluoride (WF6) gas, oxygen gas, C4F6 gas, and argon gas in the plasma processing chamber 10, and the substrate W was exposed to the plasma PL1.

[0048] In step ST3, the substrate W was taken out of the plasma processing chamber 10. This exposed the substrate W to the atmosphere. Thereafter, the substrate W was placed in the plasma processing chamber 10.

[0049] In step ST4, plasma was generated from a processing gas containing nitrogen gas in the plasma processing chamber 10, and the substrate W was exposed to the plasma.

[0050] In step ST5, the substrate W was taken out of the plasma processing chamber 10 and exposed to an aqueous ammonium solution.

[0051] (Second experiment) The second experiment was carried out in the same manner as the first experiment, except that step ST5 was not carried out.

[0052] (Third experiment) The third experiment was carried out in the same manner as the first experiment, except that step ST3 was not carried out.

[0053] (Experiment 4) The fourth experiment was carried out in the same manner as the first experiment, except that steps ST3 and ST5 were not carried out.

[0054] (5th experiment) The fifth experiment was carried out in the same manner as the first experiment, except that steps ST3 and ST4 were not carried out.

[0055] (First experiment results) First, after performing step ST2 in the first experiment and before performing step ST3, a TEM image of the cross section of the substrate W was observed. As a result, it was confirmed that a metal-containing layer DP1 and a carbon-containing layer DP2 were formed on the first region R1 of the substrate W, as shown in FIG.

[0056] Next, TEM images of the cross sections of the substrates W obtained in the first to fifth experiments were observed. As a result, in the first experiment, neither the metal-containing layer DP1 nor the carbon-containing layer DP2 was confirmed. In the second experiment, both the metal-containing layer DP1 and the carbon-containing layer DP2 were confirmed. In the third experiment, the metal-containing layer DP1 was not confirmed, but the carbon-containing layer DP2 was confirmed. In the fourth experiment, both the metal-containing layer DP1 and the carbon-containing layer DP2 were confirmed. In the fifth experiment, the metal-containing layer DP1 was not confirmed, but the carbon-containing layer DP2 was confirmed. Therefore, it can be seen that the metal-containing layer DP1 was entirely removed in the first, third, and fifth experiments in which step ST5 was performed. Furthermore, it can be seen that the carbon-containing layer DP2 was entirely removed in the first experiment in which steps ST3 and ST5 were performed.

[0057] 7 is a flowchart of a substrate processing method according to an exemplary embodiment. The substrate processing method MT2 (hereinafter referred to as "method MT2") shown in FIG. 7 can be performed by the plasma processing apparatus 1 according to the above embodiment. The method MT2 can be applied to the substrate W of FIG. 4.

[0058] Method MT2 will be described below with reference to FIGS. 4 to 7, taking as an example a case where method MT2 is applied to a substrate W using the plasma processing apparatus 1 of the above embodiment. When the plasma processing apparatus 1 is used, method MT2 can be performed in the plasma processing apparatus 1 by controlling each part of the plasma processing apparatus 1 with a control unit 2. In method MT2, a substrate W on a substrate support 11 arranged in a plasma processing chamber 10 is processed, as shown in FIG.

[0059] As shown in FIG. 7, method MT2 may include steps ST1 and ST2, steps ST13 and ST14, and step ST5. Steps ST1, ST2, ST13, ST14, and ST5 may be performed in order. Steps ST2, ST13, and ST14 may be performed in situ or in different chambers. Method MT2 may not include at least one of steps ST2, ST13, and ST5. Steps ST1, ST2, and ST5 may be performed in the same manner as in method MT1. Step ST2 may be included in step ST1. In method MT2, after step ST14 or ST5, the first region R1 located at the bottom of the recess R1a may be etched with plasma. The etching may be performed to expose the underlying region UR.

[0060] (Process ST13) In step ST13, the substrate W may be exposed to plasma generated from a hydrogen-containing gas. An example of the hydrogen-containing gas is hydrogen gas. Step ST13 may be performed in the plasma processing chamber 10.

[0061] (Process ST14) In step ST14, the substrate W may be exposed to plasma generated from a processing gas containing an oxygen-containing gas. This plasma may remove the metal-containing layer DP1. Alternatively, the carbon-containing layer DP2 may be removed. The oxygen-containing gas may be at least one of oxygen (O2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas, or carbonyl sulfide (COS) gas. The processing gas in step ST14 may further contain an inert gas. An example of the inert gas includes nitrogen gas. In the processing gas in step ST14, the flow rate of the oxygen-containing gas may be lower than the flow rate of the inert gas. This suppresses oxidation of the substrate W. Step ST14 may be performed in the plasma processing chamber 10.

[0062] In step ST14, the temperature of the substrate support 11 may be 100° C. or higher, 120° C. or higher, 130° C. or higher, or even more than 130° C., 140° C. or higher, or 150° C. or higher. The temperature of the substrate support 11 may be 250° C. or lower, or 200° C. or lower.

[0063] In step ST14, the pressure in plasma processing chamber 10 may be 1 mTorr (0.13 Pa) or more, or 10 mTorr (1.3 Pa) or more. The pressure in plasma processing chamber 10 may be 50 mTorr (6.7 Pa) or less, or 30 mTorr (4.0 Pa) or less.

[0064] 8 is an example of a timing chart showing temporal changes in bias RF power supplied to an electrode in the main body 111 of the substrate support 11 and source RF power supplied to a counter electrode. This timing chart relates to step ST14 in the method MT2. In step ST14, bias RF power LF may be supplied to the substrate support 11. The bias RF power LF may be supplied to a conductive member of the substrate support 11. In step ST14, source RF power HF for generating plasma may be supplied to the plasma processing apparatus 1. The source RF power HF may be supplied to an antenna including one or more coils.

[0065] The following is an example of the power used for a substrate W having a diameter of 300 millimeters. The bias RF power LF may be 10 W or more and 300 W or less, 30 W or more and 200 W or less, or 50 W or more and 100 W or less. The frequency of the bias RF power LF may be 100 kHz or more and 40.68 MHz or less.

[0066] The source RF power HF may be greater than or equal to 50 W and less than or equal to 1000 W, greater than or equal to 80 W and less than or equal to 800 W, or greater than or equal to 100 W and less than or equal to 500 W. The frequency of the source RF power HF may be greater than or equal to 27 MHz and less than or equal to 100 MHz.

[0067] The bias RF power LF and the source RF power HF may be applied cyclically with a period CY. The period CY may include a first period PA, a second period PB, and a third period PC. That is, step ST14 may include the first period PA, the second period PB, and the third period PC. The second period PB is the period after the first period PA. The third period PC is the period after the second period PB. In step ST14, one cycle corresponding to the period CY including the first period PA, the second period PB, and the third period PC may be repeated two or more times.

[0068] During the first period PA, the power level of the source RF power HF is maintained at a first level H3 (e.g., greater than 100 W), and the power level of the bias RF power LF is maintained at a second level L1 (e.g., less than 100 W). The second level L1 is lower than the first level H3. During the first period PA, the generation of radicals in the plasma is promoted, and thus chemical reactions between the oxygen-containing radicals and the metal-containing layer DP1 and the carbon-containing layer DP2 progress.

[0069] During the second period PB, the power level of the source RF power HF is maintained at a third level H2 (e.g., less than 200 W), and the power level of the bias RF power LF is maintained at a second level L1. The third level H2 is lower than the first level H3 and higher than the second level L1. During the second period PB, the ion flux is reduced, thereby reducing damage caused by ions to the shoulder portion SH of the recess R1a of the first region R1.

[0070] During the third period PC, the power level of the source RF power HF is maintained at a fourth level H1 (e.g., less than 100 W), and the power level of the bias RF power LF is maintained at a fifth level L2 (e.g., more than 50 W). The fourth level H1 is lower than the third level H2. The fifth level L2 is higher than the second level L1, lower than the first level H3, lower than the third level H2, and lower than the fourth level H1. During the third period PC, ions in the plasma collide with the substrate W, thereby facilitating the removal of the metal-containing layer DP1 and the carbon-containing layer DP2. By keeping the fifth level L2 low, damage caused by ions to the shoulder portion SH of the recess R1a in the first region R1 can be reduced.

[0071] The proportion of the period CY occupied by the first period PA is smaller than the proportion of the period CY occupied by the third period PC. The proportion of the period CY occupied by the first period PA may be 10% or more, or may be less than 50%. The proportion of the period CY occupied by the third period PC may be 50% or more. The frequency defining the period CY may be 0.1 kHz or more and 1 MHz or less. The time length of the period CY is the reciprocal of the frequency defining the period CY.

[0072] A DC bias may be supplied to the substrate support 11 as the electric bias instead of the bias RF power LF. The DC bias may include a voltage pulse. When the electric bias is bias RF power, the level of the electric bias is the power level of the bias RF power. When the electric bias includes a voltage pulse, the level of the electric bias is the absolute value of the negative voltage level of the voltage pulse.

[0073] According to the method MT2, the metal-containing layer DP1 can be removed by reacting with oxygen-containing chemical species. Furthermore, the carbon-containing layer DP2 can also be removed by reacting with oxygen-containing chemical species. For example, when carbon monoxide gas is used to remove the tungsten-containing layer, volatile tungsten hexacarbonyl (W(CO)6) can be generated. Using carbon monoxide gas or carbon dioxide gas as the oxygen-containing gas in step ST14 can facilitate the removal of the metal-containing layer DP1 and the carbon-containing layer DP2 compared to using oxygen gas. Furthermore, using carbon monoxide gas as the oxygen-containing gas in step ST14 can suppress etching of the first region R1 compared to using carbon dioxide gas. This suppresses the reduction of the shoulder portion SH of the recess R1a in the first region R1 and the expansion of the recess R1a.

[0074] Various experiments conducted to evaluate Method MT2 are described below, but the experiments described below are not intended to limit the present disclosure.

[0075] (Experiment 6) In the sixth experiment, a substrate W shown in FIG. 4 was prepared. The substrate W was made of silicon nitride (SiN x a first region R1 including a silicon oxide (SiO x ) and a second region R2 including the first region R1. Thereafter, the plasma processing apparatus 1 performs steps ST2 and ST14 on the substrate W.

[0076] In step ST2, plasma PL1 was generated from a processing gas containing tungsten hexafluoride (WF6) gas, oxygen gas, C4F6 gas, and argon gas in the plasma processing chamber 10, and the substrate W was exposed to the plasma PL1.

[0077] In step ST14, plasma was generated from a processing gas containing oxygen gas in the plasma processing chamber 10, and the substrate W was exposed to the plasma.

[0078] (Experiment 7) The seventh experiment was carried out in the same manner as the sixth experiment, except that in step ST14, plasma was generated from a processing gas containing oxygen gas and nitrogen gas. The flow rate of the oxygen gas was lower than the flow rate of the nitrogen gas.

[0079] (Second experiment results) TEM images of the cross sections of the substrates W obtained in the sixth and seventh experiments were observed. As a result, neither the metal-containing layer DP1 nor the carbon-containing layer DP2 was confirmed in the sixth and seventh experiments. The fourth experiment was an experiment in which oxygen gas was replaced with nitrogen gas in step ST14 of the sixth experiment. Therefore, it can be seen that the metal-containing layer DP1 and the carbon-containing layer DP2 were entirely removed in the sixth and seventh experiments in which step ST14 was performed.

[0080] (Experiment 8) The eighth experiment was carried out in the same manner as the first experiment, except that step ST3 was not carried out and step ST13 was carried out between step ST2 and step ST4.

[0081] In step ST13, plasma was generated from a processing gas containing hydrogen gas in the plasma processing chamber 10, and the substrate W was exposed to the plasma.

[0082] (Experiment 9) The ninth experiment was carried out in the same manner as the eighth experiment, except that step ST5 was not carried out.

[0083] (Third experiment results) TEM images of the cross sections of the substrates W obtained in the eighth and ninth experiments were observed. As a result, in the eighth experiment, the metal-containing layer DP1 was slightly observed, but the carbon-containing layer DP2 was not observed. In the ninth experiment, the metal-containing layer DP1 was observed, but the carbon-containing layer DP2 was not observed. Therefore, it can be seen that in the eighth experiment in which step ST5 was performed, a portion of the metal-containing layer DP1 was removed. Furthermore, it can be seen that in the eighth and ninth experiments in which steps ST13 and ST4 were performed, the entire carbon-containing layer DP2 was removed.

[0084] (Experiment 10) In the tenth experiment, a substrate W shown in FIG. 4 was prepared. The substrate W was made of silicon nitride (SiN x a first region R1 including a silicon oxide (SiO x ) and a second region R2 including the first region R1. Thereafter, the plasma processing apparatus 1 performs steps ST2 and ST14 on the substrate W.

[0085] In step ST2, plasma PL1 was generated from a process gas containing tungsten hexafluoride (WF6) gas, a hydrogen-containing gas, a fluorocarbon gas, and an argon gas in the plasma processing chamber 10, and the substrate W was exposed to the plasma PL1. The plasma PL1 formed a metal-containing layer DP1 on the first region R1 while etching the second region R2 (see FIG. 5).

[0086] In step ST14, plasma was generated from a processing gas containing nitrogen gas and oxygen gas in the plasma processing chamber 10, and the substrate W was exposed to the plasma. The metal-containing layer DP1 was removed by the plasma (see FIG. 6). In step ST14, the flow rate of the oxygen gas was lower than the flow rate of the nitrogen gas. The pressure in the plasma processing chamber 10 was 10 mTorr (1.3 Pa). The temperature of the substrate support 11 was 150°C.

[0087] In step ST14, as shown in Fig. 8, bias RF power LF and source RF power HF were applied periodically with a cycle CY. In a first period PA, the power level of the source RF power HF was maintained at 700 W, and the power level of the bias RF power LF was maintained at 0 W. In a second period PB, the power level of the source RF power HF was maintained at 100 W, and the power level of the bias RF power LF was maintained at 0 W. In a third period PC, the power level of the source RF power HF was maintained at 0 W, and the power level of the bias RF power LF was maintained at 50 W. The frequency defining the cycle CY was 0.4 kHz. The proportion of the first period PA in the cycle CY was 24%. The proportion of the third period PC in the cycle CY was 60%.

[0088] After step ST14, plasma was generated from a processing gas containing a hydrogen-containing gas, a hydrofluorocarbon gas, and an argon gas in the plasma processing chamber 10, and the substrate W was exposed to the plasma. The first region R1 located at the bottom of the recess R1a was etched by the plasma, thereby exposing the underlying region UR.

[0089] (Experiment 11) The 11th experiment was carried out in the same manner as the 10th experiment, except that carbon dioxide gas was used instead of oxygen gas in step ST14. Therefore, the processing gas contained nitrogen gas and carbon dioxide gas. The flow rate of the carbon dioxide gas was lower than the flow rate of the nitrogen gas.

[0090] (Experiment 12) The twelfth experiment was conducted in the same manner as the tenth experiment, except that carbon monoxide gas was used instead of oxygen gas in step ST14. Therefore, the processing gas contained nitrogen gas and carbon monoxide gas. The flow rate of the carbon monoxide gas was lower than the flow rate of the nitrogen gas.

[0091] (Experiment 13) The 13th experiment was carried out in the same manner as the 10th experiment, except that oxygen gas was not used in step ST14, and therefore the processing gas was nitrogen gas.

[0092] (4th Experimental Results) In Experiments 11 to 13, a TEM image of the cross section of the substrate W was observed after step ST14 and before etching the bottom of the recess R1a. Using EDS (Energy Dispersive X-ray Spectroscopy), a metal-containing layer DP1 was confirmed in Experiment 13, but not in Experiments 11 and 12. The experimental results demonstrate that the metal-containing layer DP1 can be removed by plasma generated from a processing gas containing an oxygen-containing gas.

[0093] Furthermore, the reduction in the shoulder portion SH of the recess R1a in the first region R1 was measured. The reduction is the distance between the bottom end of the shoulder portion SH and the top surface of the first region R1 in a direction perpendicular to the main surface of the substrate W. In the 13th experiment, the reduction in the shoulder portion SH was 3.5 nm. In the 11th experiment, the reduction in the shoulder portion SH was 4.1 nm. In the 12th experiment, the reduction in the shoulder portion SH was 3.9 nm. The critical dimension (CD) of the recess R1a was also measured at the bottom end of the shoulder portion SH. In the 13th experiment, the CD was 14.8 nm. In the 11th experiment, the CD was 16.8 nm. In the 12th experiment, the CD was 14.8 nm. The experimental results show that using carbon monoxide gas can reduce the reduction in the shoulder portion SH and the increase in the CD compared to using carbon dioxide gas.

[0094] (5th Experimental Results) In Experiments 11 to 13, after etching the bottom of the recess R1a, TEM images of the cross section of the substrate W and SEM images of the top surface of the substrate W were observed. In Experiment 13, residue was observed on the bottom of the recess R1a, but in Experiments 11 and 12, no residue was observed on the bottom of the recess R1a. In Experiment 10, a small amount of residue was observed on the bottom of the recess R1a. The residue was caused by the metal-containing layer DP1 remaining on the bottom of the recess R1a after step ST14. The experimental results show that the metal-containing layer DP1 on the bottom of the recess R1a can be removed by using plasma generated from a processing gas containing an oxygen-containing gas.

[0095] 9 is a diagram illustrating a substrate processing apparatus according to an exemplary embodiment, in which the method MT1 or the method MT2 may be applied to a substrate W using the substrate processing apparatus illustrated in FIG.

[0096] 9 includes a plasma processing apparatus 1, a control unit 2, and a wet processing apparatus 200. The substrate processing apparatus may include a transfer robot that transfers the substrate W between the plasma processing apparatus 1 and the wet processing apparatus 200. The control unit 2 is configured to control each unit of the plasma processing apparatus 1 and the wet processing apparatus 200. Under the control of the control unit 2, the method MT1 or the method MT2 can be performed in the substrate processing apparatus of FIG.

[0097] The wet processing apparatus 200 may include a container 210 for containing a base such as an alkaline aqueous solution, a container 212 for containing a rinse liquid, and a container 214 for containing pure water. The wet processing apparatus 200 may also include a dryer for drying the substrate W.

[0098] The wet processing apparatus 200 may include an inlet 216 for receiving the substrate W unloaded from the plasma processing apparatus 1, an outlet 218 for unloading the substrate W to the plasma processing apparatus 1, and a transfer robot 220 for transporting the substrate W. The transfer robot 220 transports the substrate W from the inlet 216 to the container 210. The transfer robot 220 transports the substrate W from the container 210 to the container 212. The transfer robot 220 transports the substrate W from the container 212 to the container 214. The transfer robot 220 transports the substrate W from the container 214 to the outlet 218.

[0099] When the method MT1 is performed in the substrate processing apparatus of FIG. 9 , steps ST1, ST2, and ST4 may be performed in the plasma processing chamber 10 of the plasma processing apparatus 1. Step ST5 may be performed in the container 210 (chamber) of the wet processing apparatus 200. In step ST5, a base is supplied to the substrate W. As a result, the metal-containing layer DP1 is removed by the base. The substrate W may be immersed in the base in the container 210. Thereafter, the substrate W may be immersed in a rinse liquid in the container 212. Thereafter, the substrate W may be immersed in pure water in the container 214. Thereafter, the substrate W may be dried in a dryer of the wet processing apparatus 200. Alternatively, the substrate W may be dried by reducing the pressure in the plasma processing chamber 10 of the plasma processing apparatus 1.

[0100] 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.

[0101] For example, the steps of method MT1 and the steps of method MT2 may be combined in any manner. Step ST13 of method MT2 may be performed between step ST2 and step ST4 of method MT1 instead of step ST3.

[0102] Various exemplary embodiments included in the present disclosure are described below in [E1] to [E19].

[0103] [E1] (a) providing a substrate, the substrate having a first region comprising a first material comprising silicon and a second region comprising a second material different from the first material; (b) etching the second region while forming a metal-containing layer on the first region using plasma generated from a process gas containing a halogen and a metal; (c) removing the metal-containing layer with a base; A substrate processing method comprising:

[0104] According to the method [E1], the metal-containing layer can be removed by reacting the metal-containing layer with a base.

[0105] [E2] (d) The substrate processing method according to [E1], further comprising the step of exposing the substrate to the atmosphere between (b) and (c).

[0106] In this case, even if a carbon-containing layer is formed on the metal-containing layer, the carbon-containing layer can be removed in (c).

[0107] [E3] (e) The substrate processing method according to [E1] or [E2], further comprising, between (b) and (c), a step of exposing the substrate to plasma generated from an inert gas.

[0108] In this case, even if a carbon-containing layer is formed on the metal-containing layer, the carbon-containing layer can be removed in (c).

[0109] [E4] The substrate processing method according to any one of [E1] to [E3], wherein (c) is performed in a chamber different from the chamber in which (b) is performed.

[0110] [E5] The substrate processing method according to any one of [E1] to [E4], wherein the processing gas further contains carbon.

[0111] [E6] The substrate processing method according to any one of [E1] to [E5], wherein the base has a pH of 11 or less.

[0112] [E7] The substrate processing method according to any one of [E1] to [E6], wherein the metal is at least one of molybdenum, tungsten, titanium, niobium, rhenium, osmium, ruthenium, platinum, germanium, and tantalum.

[0113] [E8] The substrate processing method according to any one of [E1] to [E7], wherein the processing gas contains a metal halide gas.

[0114] [E9] (a) providing a substrate, the substrate comprising a silicon-containing region having a recess, and a metal-containing layer disposed on the silicon-containing region, the metal-containing layer comprising a halogen; (b) removing the metal-containing layer with a plasma generated from a process gas including an oxygen-containing gas; A substrate processing method comprising:

[0115] According to the method [E9], the metal-containing layer can be removed by reacting the metal-containing layer containing a halogen with a chemical species containing oxygen.

[0116] [E10] The substrate processing method according to [E9], wherein in (a), the region within the recess is etched by plasma generated from a processing gas containing a halogen and a metal.

[0117] [E11] The substrate processing method according to [E9] or [E10], wherein the substrate further includes a carbon-containing layer provided on the metal-containing layer.

[0118] [E12] The substrate processing method according to any one of [E9] to [E11], wherein the processing gas in (b) further contains an inert gas.

[0119] [E13] (c) between (a) and (b), exposing the substrate to plasma generated from a hydrogen-containing gas; (d) after (b), exposing the substrate to a base; The substrate processing method according to any one of [E9] to [E12], further comprising:

[0120] [E14] The substrate processing method according to any one of [E9] to [E13], wherein the metal-containing layer contains at least one of molybdenum, tungsten, titanium, niobium, rhenium, osmium, ruthenium, platinum, germanium, and tantalum.

[0121] [E15] The substrate processing method according to any one of [E10] or [E11] to [E14] citing [E10], wherein the processing gas contains a metal halide gas.

[0122] [E16] The substrate processing method according to any one of [E9] to [E15], wherein the oxygen-containing gas is at least one of oxygen gas, carbon monoxide gas, carbon dioxide gas, and carbonyl sulfide gas.

[0123] [E17] The step (b) is (b1) setting the power level of high frequency power for generating the plasma to a first level and setting the level of an electric bias supplied to a substrate support that supports the substrate to a second level; (b2) after (b1), setting the power level of the high frequency power to a third level lower than the first level, and setting the level of the electrical bias to the second level; (b3) after (b2), setting the power level of the high frequency power to a fourth level lower than the third level, and setting the level of the electrical bias to a fifth level higher than the second level; The substrate processing method according to any one of [E9] to [E16], comprising:

[0124] [E18] a chamber; a substrate support for supporting a substrate in the chamber, the substrate comprising a silicon-containing region having a recess and a metal-containing layer disposed on the silicon-containing region, the metal-containing layer including a halogen; a gas supply configured to supply a process gas into the chamber, the process gas comprising an oxygen-containing gas; and a plasma generating unit configured to generate a plasma from the process gas within the chamber; A control unit; Equipped with The control unit is configured to control the gas supply unit and the plasma generation unit so as to remove the metal-containing layer by the plasma.

[0125] [E19] (a) providing a substrate, the substrate comprising a silicon-containing region having a recess and a metal-containing layer disposed on the silicon-containing region; (b) removing the metal-containing layer with a base; Including, The method for processing a substrate, wherein the base has a pH of 11 or less.

[0126] According to the method [E19], the metal-containing layer can be removed by reacting the metal-containing layer with a base.

[0127] 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]

[0128] 1...plasma processing apparatus, 2...controller, 10...plasma processing chamber, 11...substrate support, 12...plasma generation unit, 20...gas supply unit, DP1...metal-containing layer, PL1...plasma, R1...first region, R1a...recess, R2...second region, W...substrate

Claims

1. (a) providing a substrate, the substrate having a first region comprising a first material comprising silicon, a second region comprising a second material different from the first material, and a mask having an opening disposed over the second region; (b) etching the second region through the opening while forming a metal-containing layer on the first region using plasma generated from a process gas containing a halogen and a metal; (c) removing the metal-containing layer with a base; A substrate processing method comprising:

2. 2. The substrate processing method according to claim 1, further comprising the step of: (d) exposing the substrate to the atmosphere between (b) and (c).

3. (a) providing a substrate, the substrate having a first region comprising a first material comprising silicon and a second region comprising a second material different from the first material; (b) etching the second region while forming a metal-containing layer on the first region using plasma generated from a process gas containing a halogen and a metal; (c) removing the metal-containing layer with a base; (e) between (b) and (c), exposing the substrate to plasma generated from an inert gas; A substrate processing method comprising:

4. 3. The substrate processing method according to claim 1, wherein the step (c) is performed in a chamber different from the chamber in which the step (b) is performed.

5. The substrate processing method according to claim 1 , wherein the processing gas further contains carbon.

6. 3. The substrate processing method according to claim 1, wherein the base has a pH of 11 or less.

7. 3. The substrate processing method according to claim 1, wherein the metal is at least one of molybdenum, tungsten, titanium, niobium, rhenium, osmium, ruthenium, platinum, germanium, and tantalum.

8. 3. The substrate processing method according to claim 1, wherein the processing gas contains a metal halide gas.

9. A substrate processing method as described in claim 1 or 2, wherein the base includes at least one of ammonia, sodium carbonate, and sodium bicarbonate.

10. A method of manufacturing a semiconductor device, comprising: (a) providing a substrate, the substrate having a first region comprising a first material comprising silicon, and a second region comprising a second material different from the first material; (b) etching the second region while forming a metal-containing layer on the first region with a first plasma generated from a first process gas containing a halogen and a metal; (c) removing the metal-containing layer with a second plasma generated from a second process gas comprising an oxygen-containing gas; A substrate processing method comprising:

11. A substrate processing method as described in claim 10, wherein the first region has a recess and the second region is embedded within the recess.

12. The substrate processing method according to claim 10 , wherein in (b), a carbon-containing layer is formed on the metal-containing layer.

13. 12. The substrate processing method according to claim 10, wherein the second processing gas in (c) further contains an inert gas.

14. A method of manufacturing a semiconductor device, comprising: (a) providing a substrate, the substrate comprising a silicon-containing region having a recess; and a metal-containing layer disposed on the silicon-containing region, the metal-containing layer including a halogen; (b) removing the metal-containing layer with a plasma generated from a process gas including an oxygen-containing gas; (c) between (a) and (b), exposing the substrate to plasma generated from a hydrogen-containing gas; (d) after (b), exposing the substrate to a base; A substrate processing method comprising:

15. 12. The substrate processing method according to claim 10, wherein the metal-containing layer contains at least one of molybdenum, tungsten, titanium, niobium, rhenium, osmium, ruthenium, platinum, germanium, and tantalum.

16. The substrate processing method of claim 10 , wherein the first process gas comprises a metal halide gas.

17. 12. The substrate processing method according to claim 10, wherein the oxygen-containing gas is at least one of oxygen gas, carbon monoxide gas, carbon dioxide gas, and carbonyl sulfide gas.

18. A method of manufacturing a semiconductor device, comprising: (a) providing a substrate, the substrate comprising a silicon-containing region having a recess; and a metal-containing layer disposed on the silicon-containing region, the metal-containing layer including a halogen; (b) removing the metal-containing layer with a plasma generated from a process gas including an oxygen-containing gas; Including, The (b) is (b1) setting a power level of high frequency power for generating the plasma to a first level and a level of an electric bias supplied to a substrate support that supports the substrate to a second level; (b2) after (b1), setting the power level of the high frequency power to a third level lower than the first level, and setting the level of the electrical bias to the second level; (b3) after (b2), setting the power level of the high frequency power to a fourth level lower than the third level, and setting the level of the electrical bias to a fifth level higher than the second level; A substrate processing method comprising:

19. a chamber; a substrate support for supporting a substrate in the chamber, the substrate having a first region including a first material including silicon and a second region including a second material different from the first material; a gas supply configured to supply a first process gas and a second process gas into the chamber, the first process gas comprising a halogen and a metal, and the second process gas comprising an oxygen-containing gas; a plasma generating unit configured to generate a first plasma and a second plasma from the first process gas and the second process gas, respectively, in the chamber; A control unit; Equipped with the control unit is configured to control the gas supply unit and the plasma generation unit so as to form a metal-containing layer on the first region by the first plasma while etching the second region, and to remove the metal-containing layer by the second plasma.

20. A chamber; a substrate support for supporting a substrate in the chamber, the substrate having a first region including a first material including silicon, a second region including a second material different from the first material, and a mask having an opening disposed over the second region; a gas supply configured to supply a process gas into the chamber, the process gas including a halogen and a metal; a plasma generating unit configured to generate a plasma from the process gas within the chamber; a base supply device for supplying a base to the substrate; A control unit; Equipped with the control unit is configured to control the gas supply unit and the plasma generation unit so as to form a metal-containing layer on the first region by the plasma while etching the second region; The control unit is configured to control the base supply device so as to remove the metal-containing layer with the base.

Images