Etching method and plasma processing apparatus

Abstract

To provide an etching method and a plasma processing apparatus capable of forming a metal-containing deposit having a desired shape or a desired characteristic on a mask.SOLUTION: An etching method includes the steps of: (a) providing a substrate having an etching object film and a mask on the etching object film; (b) after (a), forming a metal-containing deposit on the mask by first plasma generated from first processing gas containing metal-containing gas and hydrogen-containing gas; (c) after (b), deforming or modifying the metal-containing deposit by a second plasma generated from a second processing gas different from the first processing gas; and (d) after (c), etching the etching object film.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] SUMMARY OF THE INVENTION Exemplary embodiments of the present disclosure relate to an etching 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 an etching method and a plasma processing apparatus that can form a metal-containing deposit on a mask with a desired shape or desired properties. [Means for solving the problem]

[0005] In one exemplary embodiment, an etching method includes: (a) providing a substrate having a film to be etched and a mask on the film to be etched; (b) after (a), forming a metal-containing deposit on the mask using a first plasma generated from a first process gas including a metal-containing gas and a hydrogen-containing gas; (c) after (b), deforming or modifying the metal-containing deposit using a second plasma generated from a second process gas different from the first process gas; and (d) after (c), etching the film to be etched. [Effects of the Invention]

[0006] According to one exemplary embodiment, an etching method and plasma processing apparatus are provided that can form a metal-containing deposit on a mask with a desired shape or desired properties. [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 flow chart of an etching 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 an etching method according to one example embodiment. [Figure 6] FIG. 6 is a cross-sectional view illustrating a step of an etching method according to one example embodiment. [Figure 7] FIG. 7 is a cross-sectional view illustrating a step of an etching method according to one example embodiment. [Figure 8] FIG. 8 is a cross-sectional view illustrating a step of an etching method according to one example embodiment. [Figure 9] FIG. 9 is a cross-sectional view of an example substrate including a metal-containing deposit modified by a second plasma under first conditions. [Figure 10] FIG. 10 is a cross-sectional view of an example substrate including a metal-containing deposit modified by a second plasma under a second condition. [Figure 11] FIG. 11 is a cross-sectional view of an example substrate including a metal-containing deposit modified by a second plasma under a third condition. [Figure 12] FIG. 12 is a cross-sectional view of an example substrate including a metal-containing deposit modified by a second plasma under a fourth condition. [Figure 13]FIG. 13 is a diagram showing an example of the surface profile of the tungsten-containing deposit in the first experiment. [Figure 14] FIG. 14 is a graph showing an example of the relationship between the thickness and the aspect ratio of the tungsten-containing deposit in the first experiment. [Figure 15] FIG. 15 is a diagram showing an example of the surface profile of the tungsten-containing deposit in the second experiment. [Figure 16] FIG. 16 is a graph showing an example of the relationship between the thickness and the aspect ratio of the tungsten-containing deposit in the second experiment. [Figure 17] FIG. 17 is a diagram showing an example of the surface profile of the tungsten-containing deposit in the third experiment. [Figure 18] FIG. 18 is a graph showing an example of the relationship between the thickness and the aspect ratio of the tungsten-containing deposit in the third experiment. [Figure 19] FIG. 19 is a diagram showing an example of the surface profile of the tungsten-containing deposit in the fourth experiment. [Figure 20] FIG. 20 is a diagram showing an example of the surface profile of the tungsten-containing deposit in the fifth experiment. DETAILED DESCRIPTION OF THE INVENTION

[0008] Various exemplary embodiments 1 to 19 will be described below.

[0009] (Embodiment 1) (a) providing a substrate having a film to be etched and a mask on the film to be etched; (b) after (a), forming a metal-containing deposit on the mask using a first plasma generated from a first process gas including a metal-containing gas and a hydrogen-containing gas; (c) after (b), transforming or modifying the metal-containing deposit with a second plasma generated from a second process gas different from the first process gas; (d) after (c), etching the etching target film; An etching method comprising:

[0010] (Embodiment 2) 2. The etching method according to claim 1, wherein (d) includes etching the target film with a third plasma generated from a third process gas different from the first process gas and the second process gas.

[0011] (Embodiment 3) 3. The etching method according to claim 1 or 2, wherein the hydrogen-containing gas comprises at least one of hydrogen gas, a hydrocarbon gas, and a hydrofluorocarbon gas.

[0012] (Embodiment 4) 4. The etching method according to any one of embodiments 1 to 3, wherein the first process gas comprises a noble gas.

[0013] (Embodiment 5) 5. The etching method according to any one of embodiments 1 to 4, wherein in (b), the temperature of a substrate support for supporting the substrate is 0°C or higher and 250°C or lower.

[0014] (Embodiment 6) 6. The etching method according to any one of embodiments 1 to 5, wherein a ratio of a flow rate of the hydrogen-containing gas to a flow rate of the metal-containing gas is 2 or more and 40 or less.

[0015] (Embodiment 7) 7. The etching method according to any one of embodiments 1 to 6, wherein the second process gas contains at least one of a fluorocarbon gas, a hydrofluorocarbon gas, and a halogen-containing gas.

[0016] (Embodiment 8) 8. The etching method of embodiment 7, wherein the second process gas includes at least one of C4F6 gas, CH3F gas, and CHF3 gas.

[0017] (Embodiment 9) 9. The etching method of embodiment 7 or 8, wherein the second process gas comprises a halogen-containing gas containing silicon.

[0018] (Embodiment 10) 10. The etching method according to any one of embodiments 7 to 9, wherein the second process gas contains NF3 gas.

[0019] (Embodiment 11) 11. The etching method according to any one of embodiments 1 to 10, wherein in (c), bias power is supplied to a substrate support for supporting the substrate.

[0020] (Embodiment 12) 12. The etching method according to any one of embodiments 1 to 11, wherein the mask comprises at least one of a silicon-containing film, a carbon-containing film, and a metal-containing film.

[0021] (Embodiment 13) 13. The etching method according to any one of embodiments 1 to 12, wherein the mask has an opening, and the aspect ratio of the opening is 1 or more and 100 or less.

[0022] (Embodiment 14) 14. The etching method according to any one of embodiments 1 to 13, wherein the film to be etched includes at least one of a silicon-containing film and a carbon-containing film.

[0023] (Embodiment 15) 15. The etching method according to embodiment 14, wherein the film to be etched comprises at least one of a silicon-containing film containing boron, a silicon film, a silicon oxide film, and a silicon nitride film.

[0024] (Embodiment 16) The etching method according to any one of embodiments 1 to 15, wherein (d) includes a step of etching the film to be etched by at least one of chemical etching using a gas without using plasma and wet etching.

[0025] (Embodiment 17) 17. The etching method according to any one of embodiments 1 to 16, wherein the metal-containing gas contains at least one of tungsten, molybdenum, and zirconium.

[0026] (Embodiment 18) (a) providing a substrate having a film to be etched, the film including a silicon-containing film, and a mask on the film to be etched; (b) after (a), forming a tungsten-containing deposit on the mask by a first plasma generated from a first process gas containing tungsten hexafluoride gas and a hydrogen-containing gas, the hydrogen-containing gas containing at least one of hydrogen gas, a hydrocarbon gas, and a hydrofluorocarbon gas; (c) after (b), transforming or modifying the tungsten-containing deposit with a second plasma generated from a second process gas different from the first process gas, the second process gas including at least one of a fluorocarbon gas, a hydrofluorocarbon gas, and a halogen-containing gas; (d) after (c), etching the target film with a third plasma generated from a third process gas different from the first process gas and the second process gas; An etching method comprising:

[0027] (Embodiment 19) a chamber; a substrate support for supporting a substrate in the chamber, the substrate having a film to be etched and a mask on the film to be etched; a gas supply unit configured to supply into the chamber a first process gas including a metal-containing gas and a hydrogen-containing gas and a second process gas different from the first process gas; a plasma generating unit configured to generate a first plasma and a second plasma from the first processing gas and the second processing gas, respectively, in the chamber; A control unit; Equipped with The control unit forming a metal-containing deposit on the mask with the first plasma; After forming the metal-containing deposit, the second plasma is used to transform or modify the metal-containing deposit; After transforming or modifying the metal-containing deposit, the target film is etched. A plasma processing apparatus configured to control the gas supply unit and the plasma generation unit.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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).

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 3 is a flowchart of an etching method according to one exemplary embodiment. The etching 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.

[0047] Fig. 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 has a film to be etched RE and a mask MK on the film to be etched RE. The film to be etched RE may be provided on an underlayer UR. The mask MK may have at least one opening OP. The aspect ratio of the opening OP may be 1 or more and 100 or less.

[0048] The etching target film RE may include at least one of a silicon-containing film and a carbon-containing film. The silicon-containing film may include at least one of a boron-containing silicon-containing film, a silicon film, a silicon oxide film, and a silicon nitride film. The silicon-containing film may be a stacked film in which silicon oxide films and silicon nitride films are alternately stacked. The carbon-containing film may be an amorphous carbon film. The etching target film RE may be a film for a memory device such as a DRAM or 3D-NAND.

[0049] The mask MK may include at least one of a silicon-containing film, a carbon-containing film, and a metal-containing film. The silicon-containing film may include at least one of a polysilicon film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film. The carbon-containing film may include at least one of an amorphous carbon film and a photoresist film. The metal-containing film may include titanium nitride (TiN x ) film, tungsten silicide (W x Si y ) film, tungsten silicon nitride (W x Si y N z ) film, tungsten silicon boron (W x Si y B z ) film and tungsten silicon carbon (W x Si y C z The composition ratios x, y, and x may be real numbers greater than 0.

[0050] The underlying film UR may contain a material different from that of the etching target film RE. The underlying film UR may contain at least one of a silicon-containing film, a carbon-containing film, and a metal-containing film.

[0051] Method MT1 will be described below with reference to FIGS. 3 to 8, 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. 5 to 8 is a cross-sectional view showing one step of an etching 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.

[0052] 3, the method MT1 may include steps ST1 to ST5. Steps ST1 to ST5 may be performed in order. The method MT1 does not necessarily have to include step ST5.

[0053] (Process ST1) 4 is provided. The substrate W may be provided in a plasma processing chamber 10. The substrate W may be supported by a substrate support 11 in the plasma processing chamber 10. An underlayer UR may be disposed between the substrate support 11 and the etching target film RE.

[0054] (Process ST2) In step ST2, as shown in FIG. 5, a metal-containing deposit DP1 is formed on the mask MK by a first plasma PL1 generated from the first process gas. The metal-containing deposit DP1 may be formed on the upper surface TP of the mask MK. The metal-containing deposit DP1 may be formed on the sidewall SD and bottom BT of the opening OP of the mask MK. The thickness of the metal-containing deposit DP1 on the upper surface TP of the mask MK may be greater than the thickness of the metal-containing deposit DP1 on the sidewall SD of the opening OP of the mask MK. The metal-containing deposit DP1 may include at least one of a tungsten-containing deposit, a molybdenum-containing deposit, and a zirconium-containing deposit. The metal-containing deposit DP1 may include fluorine. The metal-containing deposit DP1 may include a WF bond.

[0055] The first process gas includes a metal-containing gas and a hydrogen-containing gas. The metal-containing gas may include at least one of a tungsten-containing gas, a molybdenum-containing gas, and a zirconium-containing gas. The tungsten-containing gas may include at least one of tungsten hexafluoride (WF6) gas, tungsten hexabromide (WBr6) gas, tungsten hexachloride (WCl6) gas, WF5Cl gas, and tungsten hexacarbonyl (W(CO)6) gas. The molybdenum-containing gas may include molybdenum hexafluoride (MoF6) gas. The zirconium-containing gas may include zirconium fluoride gas. The hydrogen-containing gas may include at least one of hydrogen (H2) gas, a hydrocarbon gas, and a hydrofluorocarbon gas. The hydrogen-containing gas may include at least one of hydrogen gas, CH4 gas, CH3F gas, C2H2 gas, C3H6 gas, and C2H4 gas. The first process gas may include a noble gas. An example of a noble gas includes argon.

[0056] In step ST2, the temperature of the substrate support 11 for supporting the substrate W may be 0°C or higher and 250°C or lower, or 10°C or higher and 120°C or lower.

[0057] The ratio of the flow rate of the hydrogen-containing gas to the flow rate of the metal-containing gas may be 2 or more and 40 or less, or may be 2 or more and 20 or less.

[0058] Step ST2 can be performed as follows: First, the gas supply unit 20 supplies a first processing gas into the plasma processing chamber 10. Next, the plasma generation unit 12 generates a first plasma PL1 from the first processing 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 first plasma PL1 forms a metal-containing deposit DP1 on the mask MK.

[0059] (Process ST3) In step ST3, as shown in FIG. 6, the metal-containing deposit DP1 is transformed or modified by a second plasma PL2 generated from the second process gas. This results in a transformed or modified metal-containing deposit DP2. The transformation refers to changing the shape of all or part of the metal-containing deposit, particularly the shape (profile) of at least the surface of the metal-containing deposit. The modification refers to changing the chemical composition of all or part of the metal-containing deposit, particularly the chemical composition of at least the surface of the metal-containing deposit. When the metal-containing deposit DP1 is transformed, the surface profile of the metal-containing deposit DP2 is different from the surface profile of the metal-containing deposit DP1. The material at the surface of the metal-containing deposit DP2 may be the same as the material at the surface of the metal-containing deposit DP1. When the metal-containing deposit DP1 is modified, the material at the surface of the metal-containing deposit DP2 is different from the material at the surface of the metal-containing deposit DP1. The material at the surface of the metal-containing deposit DP2 is obtained by reacting the active species in the second plasma PL2 with the material at the surface of the metal-containing deposit DP1. The vicinity of the surface of the metal-containing deposit DP1 may be modified. The metal-containing deposit DP1 may contain tungsten, and the second process gas may contain a halogen-containing gas containing silicon. In this case, a metal-containing deposit DP2 containing tungsten silicide is obtained. The metal-containing deposit DP1 may contain tungsten, and the second process gas may contain at least one of a fluorocarbon gas and a hydrofluorocarbon gas. In this case, a metal-containing deposit DP2 containing tungsten carbide is obtained. The metal-containing deposit DP1 may contain tungsten, and the second process gas may contain an oxygen-containing gas. In this case, a metal-containing deposit DP2 containing tungsten oxide is obtained. The surface profile of the metal-containing deposit DP2 may be the same as or different from the surface profile of the metal-containing deposit DP1.

[0060] The second process gas is different from the first process gas. Between step ST2 and step ST3, the supply of the first process gas may be stopped and the supply of the second process gas may be started. The second process gas may not contain tungsten. The second process gas may contain at least one of carbon and halogen. The second process gas may contain at least one of a fluorocarbon gas, a hydrofluorocarbon gas, and a halogen-containing gas. The second process gas may contain at least one of C4F6 gas, CH3F gas, and CHF3 gas. The second process gas may contain a halogen-containing gas containing silicon. The second process gas may contain a chlorine-containing gas containing silicon or a fluorine-containing gas containing silicon. The second process gas may contain at least one of SiCl4 gas, Si2Cl6 gas, and SiF4 gas. The second process gas may contain nitrogen trifluoride (NF3) gas. The second process gas may contain a chlorine-containing gas. The second process gas may contain chlorine (Cl2) gas. The second process gas may include at least one of an inert gas and an oxygen-containing gas. Examples of inert gases include noble gases and nitrogen gas. Examples of oxygen-containing gases include oxygen gas and carbon monoxide gas.

[0061] In step ST3, bias power may or may not be supplied to the substrate support 11 for supporting the substrate W. The processing time for step ST3 may be shorter than the processing time for step ST2. The processing time for step ST3 may be 10 seconds or more and 200 seconds or less. In step ST3, the temperature of the substrate support 11 for supporting the substrate W may be 10°C or more and 120°C or less, or 30°C or more and 80°C or less.

[0062] Step ST3 can be performed as follows: First, the gas supply unit 20 supplies a second processing gas into the plasma processing chamber 10. Next, the plasma generation unit 12 generates a second plasma PL2 from the second processing 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 plasma PL2 deforms or modifies the metal-containing deposit DP1.

[0063] Step ST3 may be performed in the same plasma processing chamber 10 as that of step ST2, or may be performed in a plasma processing chamber different from that of step ST2.

[0064] (Process ST4) In step ST4, the etching target film RE is etched. A recess RS may be formed in the etching target film RE. The recess RS has a shape corresponding to the opening OP of the mask MK. The bottom of the recess RS may or may not reach the base film UR.

[0065] 7, step ST4 may include a step of etching the etching target film RE with a third plasma PL3 generated from a third process gas. The third process gas is different from the first process gas and the second process gas. Between step ST3 and step ST4, the supply of the second process gas may be stopped and the supply of the third process gas may be started.

[0066] Step ST4 can be performed as follows: First, the gas supply unit 20 supplies a third process gas into the plasma processing chamber 10. Next, the plasma generation unit 12 generates a third plasma PL3 from the third 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 etching target film RE is etched with the third plasma PL3.

[0067] 8, step ST4 may include etching the etching target film RE by at least one of chemical etching using gas without using plasma and wet etching. In this case, step ST4 may be performed as follows: First, the substrate W is removed from the plasma processing chamber 10. Next, the substrate W is provided in a wet etching apparatus. In the wet etching apparatus, the etching target film RE is etched with an etchant.

[0068] Step ST4 may be performed in the same plasma processing chamber 10 as step ST2, or in a different plasma processing chamber from step ST2. Step ST4 may be performed in the same plasma processing chamber as step ST3, or in a different plasma processing chamber from step ST3. For example, step ST2 may use a CCP chamber, step ST3 may use an ICP chamber, and step ST4 may use either a CCP chamber or an ICP chamber. A transfer module may be provided between two or more chambers, and the transfer module may include a transfer chamber whose internal space can be depressurized. Using such a transfer module allows the substrate W to be transferred between chambers without breaking the vacuum environment.

[0069] (Process ST5) In step ST5, steps ST2 to ST4 are repeated until a termination condition is met. For example, step ST5 may be terminated when the number of times one cycle including steps ST2 to ST4 has been executed reaches a threshold value.

[0070] The above-described plasma processing apparatus 1 and method MT1 can form a metal-containing deposit DP2 (see FIG. 6) having a desired shape or desired properties on the mask MK, thereby controlling the shape of the recess RS formed in step ST4.

[0071] 9 is a cross-sectional view of an example substrate including a metal-containing deposit transformed by the second plasma under the first condition. Under the first condition, bias power is supplied to the substrate support 11 in step ST3. The second process gas includes at least one of C4F6 gas, CH3F gas, and CHF3 gas.

[0072] As shown in FIG. 9, under the first condition, a metal-containing deposit DP21 is obtained as an example of the metal-containing deposit DP2 in FIG. 6. Under the first condition, the metal-containing deposit tends to deposit on the sidewall SD of the opening OP of the mask MK. Before step ST3, the thickness of the metal-containing deposit DP1 on the upper surface TP of the mask MK is greater than the thickness of the metal-containing deposit DP1 on the sidewall SD of the opening OP of the mask MK. Therefore, after step ST3, the metal-containing deposit DP21, which is a nearly conformal film, is obtained. The metal-containing deposit DP21 may have substantially the same thickness on the upper surface TP of the mask MK and on the sidewall SD of the opening OP.

[0073] The mechanism by which the metal-containing deposit DP21 having the above-described shape is obtained is presumed to be as follows, but is not limited to this. In step ST3, the metal-containing deposit DP1 on the upper surface TP of the mask MK is sputtered by bias power. The sputtered particles then re-adhere to the sidewalls SD of the openings OP of the mask MK. This causes the metal-containing deposit DP1 on the upper surface TP of the mask MK to become thinner, while the metal-containing deposit DP1 on the sidewalls SD of the openings OP of the mask MK to become thicker. As a result, the metal-containing deposit DP21 having the above-described shape is obtained.

[0074] 10 is a cross-sectional view of an example substrate including a metal-containing deposit transformed by the second plasma under a second condition, in which no bias power is supplied to the substrate support 11 in step ST3. The second process gas includes at least one of C4F6 gas, CH3F gas, and CHF3 gas.

[0075] As shown in FIG. 10, under the second conditions, a metal-containing deposit DP22 is obtained as an example of the metal-containing deposit DP2 in FIG. 6. Under the second conditions, the metal-containing deposit on the sidewall SD of the opening OP of the mask MK is less likely to be etched and tends not to increase. Before step ST3, the thickness of the metal-containing deposit DP1 on the upper surface TP of the mask MK is greater than the thickness of the metal-containing deposit DP1 on the sidewall SD of the opening OP of the mask MK. Therefore, after step ST3, the metal-containing deposit DP22 has a first thickness on the upper surface TP of the mask MK and a second thickness, which is smaller than the first thickness, on the sidewall SD of the opening OP of the mask MK.

[0076] The mechanism by which the metal-containing deposit DP22 having the above-described shape is obtained is presumed to be, but is not limited to, the following. In step ST3, since no bias power is supplied to the substrate support 11, sputtering of the metal-containing deposit DP1 on the upper surface TP of the mask MK is unlikely to occur. As a result, the metal-containing deposit DP22 having the above-described shape is obtained.

[0077] 11 is a cross-sectional view of an example substrate including a metal-containing deposit modified by a second plasma under a third condition, where the second process gas includes a halogen-containing gas that includes silicon.

[0078] 11, under the third condition, a metal-containing deposit DP23 is obtained as an example of the metal-containing deposit DP2 in FIG. 6. Under the third condition, the metal-containing deposit on the sidewall SD of the opening OP of the mask MK tends to be etched. On the other hand, the metal-containing deposit DP1 on the upper surface TP of the mask MK and the bottom BT of the opening OP is difficult to etch. Therefore, after step ST3, the metal-containing deposit DP23 does not have a thickness on the sidewall SD of the opening OP of the mask MK.

[0079] The mechanism by which the metal-containing deposit DP23 having the above-described shape is obtained is presumed to be, but is not limited to, the following. In step ST3, activated species containing silicon and halogen react with the metal-containing deposit DP1 on the sidewall SD of the opening OP of the mask MK. For example, the fluorine composition ratio in the metal-containing deposit DP1 on the sidewall SD is greater than the fluorine composition ratio in the metal-containing deposit DP1 on the upper surface TP of the mask MK. In this case, the radicals containing silicon and chlorine react with fluorine, thereby selectively etching the metal-containing deposit DP1 on the sidewall SD.

[0080] 12 is a cross-sectional view of an example substrate including a metal-containing deposit modified by a second plasma under a fourth condition, in which the second process gas includes NF3 gas.

[0081] 12, under the fourth condition, a metal-containing deposit DP24 is obtained as an example of the metal-containing deposit DP2 in Fig. 6. Under the fourth condition, the metal-containing deposit DP24 tends to be less likely to be formed on the upper surface TP of the mask MK.

[0082] The mechanism by which the metal-containing deposit DP24 having the above-described shape is obtained is presumed to be, but is not limited to, the following. In step ST3, the metal-containing deposit DP1 on the upper surface TP of the mask MK is etched. Under the fourth condition, the carbon content in the second process gas is low, making it difficult for a carbon-containing deposit to form on the upper surface TP of the mask MK. Therefore, the amount of etching of the metal-containing deposit DP1 on the upper surface TP of the mask MK increases. On the other hand, the metal-containing deposit DP1 on the sidewall SD and bottom BT of the opening OP of the mask MK is difficult to etch. As a result, the metal-containing deposit DP24 having the above-described shape is obtained.

[0083] In step ST3, two or more of the first to fourth conditions shown in Figures 9 to 12 may be combined, thereby improving the degree of freedom in controlling the shape of the metal-containing deposit.

[0084] Although various exemplary embodiments have been described above, the present disclosure is not limited to the above-described exemplary embodiments and various additions, omissions, substitutions, and modifications may be made. Furthermore, elements of different embodiments can be combined to form other embodiments. For example, a method for manufacturing a semiconductor device including the etching method described in any one of the above-described embodiments 1 to 17 is also included in the present disclosure.

[0085] Various experiments performed to evaluate Method MT1 are described below, but the experiments described below are not intended to limit the present disclosure.

[0086] (First experiment) In the first experiment, a substrate having a silicon film and a mask on the silicon film was prepared. The mask was a silicon oxide film with an opening. The substrate was then placed in a plasma processing chamber of a plasma processing apparatus.

[0087] Next, a first plasma generated from a first process gas containing WF, Ar, and H was used to form tungsten-containing deposits on the mask, including the top surface of the mask, the sidewalls of the openings, and the bottom wall.

[0088] The substrate was then exposed to a second plasma generated from a second process gas containing C4F6 gas, Ar gas, and O2 gas for 60 seconds or 120 seconds. A capacitively coupled plasma processing system was used as the plasma processing system. Bias power was applied to the substrate support. In this manner, the tungsten-containing deposit was deformed.

[0089] (First experiment results) FIG. 13 shows an example of the surface profile of the tungsten-containing deposit in the first experiment. Profile PR0 shows the surface profile of the mask in the cross section of the substrate. Profile PR0 shows the top surface of the mask and the sidewalls and bottom of the opening in the mask. Profiles PR1 to PR3 show the surface profile of the tungsten-containing deposit in the cross section of the substrate. Profile PR1 shows the surface of the tungsten-containing deposit formed by the first plasma. Profile PR2 shows the surface of the tungsten-containing deposit transformed after exposing the substrate to the second plasma for 60 seconds. Profile PR3 shows the surface of the tungsten-containing deposit transformed after exposing the substrate to the second plasma for 120 seconds.

[0090] As shown in FIG. 13, profiles PR2 and PR3 have a greater thickness of tungsten-containing deposits on the sidewalls of the mask openings than profile PR1. Profiles PR2 and PR3 have a smaller thickness of tungsten-containing deposits on the top surface of the mask than profile PR1. Profile PR2 shows that the tungsten-containing deposits are a nearly conformal film. Profile PR3 has zero thickness of tungsten-containing deposits at the bottom of the mask openings.

[0091] FIG. 13 shows that exposing the substrate to the second plasma of the first experiment etches the tungsten-containing deposits on the top surface of the mask and at the bottom of the mask openings, while forming tungsten-containing deposits on the sidewalls of the mask openings.

[0092] FIG. 14 is a graph showing an example of the relationship between the thickness and aspect ratio of a tungsten-containing deposit in Experiment 1. The vertical axis of the graph shows the normalized thickness (nm) of the tungsten-containing deposit at the bottom of the mask opening. The normalized thickness is the ratio of the thickness of the tungsten-containing deposit at the bottom of the mask opening to the thickness of the tungsten-containing deposit on the top surface of the mask. The horizontal axis of the graph shows the aspect ratio of the mask opening. Plot DA1 shows the thickness calculated for profile PR1 in FIG. 13. Plot DA2 shows the thickness calculated for profile PR2 in FIG. 13. Plot DA3 shows the thickness calculated for profile PR3 in FIG. 13.

[0093] 14 shows that the normalized thickness of the tungsten-containing deposit at the bottom of the mask opening decreases as the exposure time of the substrate to the second plasma in the first experiment increases. It also shows that the normalized thickness of the tungsten-containing deposit at the bottom of the mask opening decreases as the aspect ratio increases. This is thought to be because, when the mask aspect ratio is high, it becomes difficult for activated species in the first plasma to reach the bottom of the mask opening when forming the tungsten-containing deposit with the first plasma.

[0094] (Second experiment) The second experiment was conducted in the same manner as the first experiment, except for the process of deforming the tungsten-containing deposit. In the second experiment, the substrate was exposed to a second plasma generated from a second process gas containing CH3F gas, CHF3 gas, NF3 gas, N2 gas, and Ar gas for 30 seconds or 60 seconds. An inductively coupled plasma processing apparatus was used as the plasma processing apparatus. No bias power was applied to the substrate support. In this manner, the tungsten-containing deposit was deformed.

[0095] (Second experiment results) Figure 15 shows an example of a surface profile of the tungsten-containing deposit in the second experiment. Profiles PR0 and PR1 are the same as profiles PR0 and PR1 in Figure 13. Profile PR12 shows the surface of the modified tungsten-containing deposit in a cross section of the substrate after exposing the substrate to the second plasma for 30 seconds. Profile PR13 shows the surface of the modified tungsten-containing deposit in a cross section of the substrate after exposing the substrate to the second plasma for 60 seconds.

[0096] 15, the thickness of the tungsten-containing deposits on the top surface of the mask and at the bottom of the mask openings is smaller in profiles PR12 and PR13 than in profile PR1. Meanwhile, the thickness of the tungsten-containing deposits on the sidewalls of the mask openings is almost unchanged in profiles PR1, PR12, and PR13.

[0097] FIG. 15 shows that exposing the substrate to the second plasma in the second experiment etches the tungsten-containing deposits on the top surface of the mask and the bottom of the mask opening, while suppressing etching of the tungsten-containing deposits on the sidewalls of the mask opening.

[0098] Figure 16 is a graph showing an example of the relationship between the thickness and aspect ratio of a tungsten-containing deposit in Experiment 2. The vertical and horizontal axes of the graph are the same as those of the graph in Figure 14. Plot DA1 shows the thickness calculated for profile PR1 in Figure 15. Plot DA12 shows the thickness calculated for profile PR12 in Figure 15. Plot DA13 shows the thickness calculated for profile PR13 in Figure 15.

[0099] 16 shows that the normalized thickness of the tungsten-containing deposit at the bottom of the mask opening decreases as the exposure time of the substrate to the second plasma in the second experiment increases. It also shows that the normalized thickness of the tungsten-containing deposit at the bottom of the mask opening decreases as the aspect ratio increases. This is thought to be because, when the mask aspect ratio is high, it becomes difficult for activated species in the first plasma to reach the bottom of the mask opening when forming the tungsten-containing deposit with the first plasma.

[0100] (Third experiment) The third experiment was conducted in the same manner as the first experiment, except for the process of deforming the tungsten-containing deposit. In the third experiment, the substrate was exposed for 60 seconds to a second plasma generated from a second process gas containing SiCl4 gas, Cl2 gas, and Ar gas. An inductively coupled plasma processing apparatus was used as the plasma processing apparatus. No bias power was applied to the substrate support. In this manner, the tungsten-containing deposit was deformed.

[0101] (Third experiment results) Figure 17 shows an example of the surface profile of the tungsten-containing deposit in Experiment 3. Profiles PR0 and PR1 are the same as profiles PR0 and PR1 in Figure 13. Profile PR22 shows the surface of the deformed tungsten-containing deposit in a cross section of the substrate.

[0102] 17, the thickness of the tungsten-containing deposit on the sidewall of the mask opening is smaller in profile PR22 than in profile PR1. Meanwhile, the thickness of the tungsten-containing deposit on the top surface of the mask and at the bottom of the mask opening remains almost unchanged between profiles PR1 and PR22.

[0103] FIG. 17 shows that exposing the substrate to the second plasma in the third experiment etched the tungsten-containing deposits on the sidewalls of the mask openings while suppressing etching of the tungsten-containing deposits on the top surface of the mask and the bottom of the mask openings.

[0104] Figure 18 is a graph showing an example of the relationship between the thickness and aspect ratio of a tungsten-containing deposit in Experiment 3. The vertical and horizontal axes of the graph are the same as those of the graph in Figure 14. Plot DA1 shows the thickness calculated for profile PR1 in Figure 17. Plot DA22 shows the thickness calculated for profile PR22 in Figure 17.

[0105] 18 shows that the normalized thickness of the tungsten-containing deposit at the bottom of the mask opening remains almost unchanged even when the substrate is exposed to the second plasma in the third experiment. It also shows that the normalized thickness of the tungsten-containing deposit at the bottom of the mask opening decreases as the aspect ratio increases. This is thought to be because, when the mask aspect ratio is high, it becomes difficult for activated species in the first plasma to reach the bottom of the mask opening when forming the tungsten-containing deposit with the first plasma.

[0106] (Experiment 4) The fourth experiment was conducted in the same manner as the first experiment, except for the process of deforming the tungsten-containing deposit. In the fourth experiment, the substrate was exposed for 60 seconds to a second plasma generated from a second process gas containing Cl gas, NF gas, Ar gas, and O gas. An inductively coupled plasma processing apparatus was used as the plasma processing apparatus. No bias power was applied to the substrate support. In this manner, the tungsten-containing deposit was deformed.

[0107] (4th Experimental Results) Figure 19 shows an example of a surface profile of the tungsten-containing deposit in Experiment 4. Profiles PR0 and PR1 are the same as profiles PR0 and PR1 in Figure 13. Profile PR32 shows the surface of the deformed tungsten-containing deposit in a cross section of the substrate.

[0108] 19, the thickness of the tungsten-containing deposit on the top surface of the mask is smaller in profile PR32 than in profile PR1. On the other hand, the thickness of the tungsten-containing deposit on the sidewalls and bottom of the opening in the mask is almost unchanged between profiles PR1 and PR32.

[0109] FIG. 19 shows that exposing the substrate to the second plasma in the fourth experiment allows etching of the tungsten-containing deposits on the top surface of the mask while suppressing etching of the tungsten-containing deposits on the sidewalls and bottom of the openings in the mask.

[0110] (5th experiment) Experiment 5 was performed in the same manner as Experiment 1, except for the process of deforming the tungsten-containing deposit. Experiment 5 performed both the process of deforming the tungsten-containing deposit in Experiment 3 and the process of deforming the tungsten-containing deposit in Experiment 2. Specifically, the substrate was exposed to a second plasma generated from a second process gas containing SiCl gas, Cl gas, and Ar gas. The substrate was then exposed to a second plasma generated from a second process gas containing CHF gas, CHF gas, NF gas, N gas, and Ar gas. An inductively coupled plasma processing apparatus was used as the plasma processing apparatus. No bias power was applied to the substrate support. In this manner, the tungsten-containing deposit was deformed.

[0111] (5th Experimental Results) Figure 20 shows an example of a surface profile of the tungsten-containing deposit in Experiment 5. Profiles PR0 and PR1 are the same as profiles PR0 and PR1 in Figure 13. Profile PR42 shows the surface of the deformed tungsten-containing deposit in a cross section of the substrate.

[0112] 20, profile PR42 has a smaller thickness of the tungsten-containing deposit on the sidewalls and bottom of the mask opening than profile PR1. Profile PR42 does not have a significantly smaller thickness of the tungsten-containing deposit on the top surface of the mask.

[0113] FIG. 20 shows that exposing the substrate to the second plasma in the fifth experiment allows etching of the tungsten-containing deposits on the sidewalls and bottom of the openings in the mask while suppressing etching of the tungsten-containing deposits on the top surface of the mask.

[0114] 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]

[0115] 1...plasma processing apparatus, 2...control unit, 10...plasma processing chamber, 11...substrate support unit, 12...plasma generation unit, 20...gas supply unit, DP1, DP2, DP21, DP22, DP23, DP24...metal-containing deposits, MK...mask, PL1...first plasma, PL2...second plasma, RE...film to be etched, W...substrate.

Claims

1. (a) providing a substrate having a film to be etched and a mask on the film to be etched; (b) after (a), forming a metal-containing deposit on the mask using a first plasma generated from a first process gas including a metal-containing gas and a hydrogen-containing gas; (c) after (b), transforming or modifying the metal-containing deposit with a second plasma generated from a second process gas different from the first process gas; (d) after (c), etching the etching target film so as to remove the deformed or modified metal-containing deposit; An etching method comprising:

2. (a) providing a substrate having a film to be etched and a mask on the film to be etched; (b) after (a), forming a metal-containing deposit on the mask using a first plasma generated from a first process gas including a metal-containing gas and a hydrogen-containing gas; (c) after (b), a step of deforming or modifying the metal-containing deposit with a second plasma generated from a second process gas different from the first process gas, wherein the deformed or modified metal-containing deposit remains at the bottom of the opening in the mask; (d) after (c), etching the etching target film; An etching method comprising:

3. (a) providing a substrate having a film to be etched and a mask on the film to be etched; (b) after (a), forming a metal-containing deposit on the mask using a first plasma generated from a first process gas including a metal-containing gas and a hydrogen-containing gas; (c) after (b), transforming or modifying the metal-containing deposit with a second plasma generated from a second process gas different from the first process gas; (d) after (c), etching the etching target film; Including, An etching method, wherein, before (c), a thickness of the metal-containing deposit on the upper surface of the mask is greater than a thickness of the metal-containing deposit on the sidewalls of the openings in the mask.

4. 4. The etching method according to claim 1, wherein (d) includes a step of etching the target film with a third plasma generated from a third process gas different from the first process gas and the second process gas.

5. 4. The etching method according to claim 1, wherein the hydrogen-containing gas contains at least one of hydrogen gas, a hydrocarbon gas, and a hydrofluorocarbon gas.

6. 4. The etching method according to claim 1, wherein the first process gas comprises a noble gas.

7. 4. The etching method according to claim 1, wherein in (b), a temperature of a substrate support part for supporting the substrate is 0° C. or higher and 250° C. or lower.

8. 4. The etching method according to claim 1, wherein a ratio of a flow rate of the hydrogen-containing gas to a flow rate of the metal-containing gas is 2 or more and 40 or less.

9. 4. The etching method according to claim 1, wherein the second process gas includes at least one of a fluorocarbon gas, a hydrofluorocarbon gas, and a halogen-containing gas.

10. The second process gas is C ４ F ６ Gas, CH ３ F gas and CHF ３ 10. The etching method of claim 9, comprising at least one of a gas.

11. 10. The etching method of claim 9, wherein the second process gas comprises a halogen-containing gas that includes silicon.

12. The second process gas is NF ３ The etching method of claim 9 including a gas.

13. 4. The etching method according to claim 1, wherein in (c), bias power is supplied to a substrate support for supporting the substrate.

14. 4. The etching method according to claim 1, wherein the mask includes at least one of a silicon-containing film, a carbon-containing film, and a metal-containing film.

15. 2. The etching method according to claim 1, wherein the mask has an opening, and the aspect ratio of the opening is 1 or more and 100 or less.

16. An etching method as described in claim 2 or 3, wherein the aspect ratio of the opening is greater than or equal to 1 and less than or equal to 100.

17. 4. The etching method according to claim 1, wherein the film to be etched includes at least one of a silicon-containing film and a carbon-containing film.

18. 18. The etching method of claim 17, wherein the film to be etched includes at least one of a silicon-containing film containing boron, a silicon film, a silicon oxide film, and a silicon nitride film.

19. 4. The etching method according to claim 1, wherein (d) includes a step of etching the film to be etched by at least one of chemical etching using a gas without using plasma and wet etching.

20. 4. The etching method according to claim 1, wherein the metal-containing gas contains at least one of tungsten, molybdenum, and zirconium.

21. (a) providing a substrate having a film to be etched, the film including a silicon-containing film, and a mask on the film to be etched; (b) after (a), forming a tungsten-containing deposit on the mask by a first plasma generated from a first process gas containing tungsten hexafluoride gas and a hydrogen-containing gas, the hydrogen-containing gas containing at least one of hydrogen gas, a hydrocarbon gas, and a hydrofluorocarbon gas; (c) after (b), transforming or modifying the tungsten-containing deposit with a second plasma generated from a second process gas different from the first process gas, the second process gas including at least one of a fluorocarbon gas, a hydrofluorocarbon gas, and a halogen-containing gas; (d) after (c), etching the etching target film so as to remove the deformed or modified tungsten-containing deposits using a third plasma generated from a third process gas different from the first process gas and the second process gas; An etching method comprising:

22. (a) providing a substrate having a film to be etched, the film comprising a silicon-containing film, and a mask on the film to be etched; (b) after (a), forming a tungsten-containing deposit on the mask by a first plasma generated from a first process gas containing tungsten hexafluoride gas and a hydrogen-containing gas, the hydrogen-containing gas containing at least one of hydrogen gas, a hydrocarbon gas, and a hydrofluorocarbon gas; (c) after (b), modifying or altering the tungsten-containing deposit with a second plasma generated from a second process gas different from the first process gas, the second process gas including at least one of a fluorocarbon gas, a hydrofluorocarbon gas, and a halogen-containing gas, and the modified tungsten-containing deposit remains at the bottom of the opening in the mask; and (d) after (c), etching the etching target film with a third plasma generated from a third process gas different from the first process gas and the second process gas; An etching method comprising:

23. (a) providing a substrate having a film to be etched, the film comprising a silicon-containing film, and a mask on the film to be etched; (b) after (a), forming a tungsten-containing deposit on the mask by a first plasma generated from a first process gas containing tungsten hexafluoride gas and a hydrogen-containing gas, the hydrogen-containing gas containing at least one of hydrogen gas, a hydrocarbon gas, and a hydrofluorocarbon gas; (c) after (b), transforming or modifying the tungsten-containing deposit with a second plasma generated from a second process gas different from the first process gas, the second process gas including at least one of a fluorocarbon gas, a hydrofluorocarbon gas, and a halogen-containing gas; (d) after (c), etching the etching target film with a third plasma generated from a third process gas different from the first process gas and the second process gas; Including, and (c) forming a tungsten-containing deposit on a top surface of the mask that is thicker than a tungsten-containing deposit on a sidewall of the opening in the mask.

24. a chamber; a substrate support for supporting a substrate in the chamber, the substrate having a film to be etched and a mask on the film to be etched; a gas supply unit configured to supply into the chamber a first process gas including a metal-containing gas and a hydrogen-containing gas and a second process gas different from the first process 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 forming a metal-containing deposit on the mask with the first plasma; After forming the metal-containing deposit, the second plasma is used to transform or modify the metal-containing deposit; After the metal-containing deposit is deformed or modified, the etching target film is etched so that the deformed or modified metal-containing deposit is removed. A plasma processing apparatus configured to control the gas supply unit and the plasma generation unit.

25. A chamber; a substrate support for supporting a substrate in the chamber, the substrate having a film to be etched and a mask on the film to be etched; a gas supply unit configured to supply into the chamber a first process gas including a metal-containing gas and a hydrogen-containing gas and a second process gas different from the first process 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 forming a metal-containing deposit on the mask with the first plasma; After forming the metal-containing deposit, the metal-containing deposit is deformed or modified by the second plasma, and the deformed or modified metal-containing deposit remains at the bottom of the opening in the mask; After transforming or modifying the metal-containing deposit, the target film is etched. A plasma processing apparatus configured to control the gas supply unit and the plasma generation unit.

26. A chamber; a substrate support for supporting a substrate in the chamber, the substrate having a film to be etched and a mask on the film to be etched; a gas supply unit configured to supply into the chamber a first process gas including a metal-containing gas and a hydrogen-containing gas and a second process gas different from the first process 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 forming a metal-containing deposit on the mask with the first plasma; After forming the metal-containing deposit, the second plasma is used to transform or modify the metal-containing deposit; After transforming or modifying the metal-containing deposit, the target film is etched. configured to control the gas supply unit and the plasma generation unit, The plasma processing apparatus, wherein, before the metal-containing deposit is deformed or modified, a thickness of the metal-containing deposit on the top surface of the mask is greater than a thickness of the metal-containing deposit on a sidewall of an opening in the mask.

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