WO2023127820A1 - エッチング方法及びプラズマ処理装置 - Google Patents

エッチング方法及びプラズマ処理装置 Download PDF

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Publication number
WO2023127820A1
WO2023127820A1 PCT/JP2022/047980 JP2022047980W WO2023127820A1 WO 2023127820 A1 WO2023127820 A1 WO 2023127820A1 JP 2022047980 W JP2022047980 W JP 2022047980W WO 2023127820 A1 WO2023127820 A1 WO 2023127820A1
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WO
WIPO (PCT)
Prior art keywords
gas
tungsten
plasma
etching method
mask
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Ceased
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PCT/JP2022/047980
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English (en)
French (fr)
Japanese (ja)
Inventor
広記 向山
幕樹 戸村
嘉英 木原
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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Application filed by Tokyo Electron Ltd filed Critical Tokyo Electron Ltd
Priority to KR1020247024131A priority Critical patent/KR20240121327A/ko
Priority to JP2023571025A priority patent/JPWO2023127820A1/ja
Priority to CN202280084991.9A priority patent/CN118435328A/zh
Publication of WO2023127820A1 publication Critical patent/WO2023127820A1/ja
Priority to US18/757,575 priority patent/US20240355589A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/40—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials
    • H10P76/408—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials characterised by their sizes, orientations, dispositions, behaviours or shapes
    • H10P76/4085—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials characterised by their sizes, orientations, dispositions, behaviours or shapes characterised by the processes involved to create the masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/3244—Gas supply means
    • H01J37/32449—Gas control, e.g. control of the gas flow
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
    • H10P50/24—Dry etching; Plasma etching; Reactive-ion etching of semiconductor materials
    • H10P50/242—Dry etching; Plasma etching; Reactive-ion etching of semiconductor materials of Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/71—Etching of wafers, substrates or parts of devices using masks for conductive or resistive materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/73—Etching of wafers, substrates or parts of devices using masks for insulating materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0402—Apparatus for fluid treatment
    • H10P72/0418—Apparatus for fluid treatment for etching
    • H10P72/0421—Apparatus for fluid treatment for etching for drying etching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/40—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials
    • H10P76/405—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials characterised by their composition, e.g. multilayer masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/32—Processing objects by plasma generation
    • H01J2237/33—Processing objects by plasma generation characterised by the type of processing
    • H01J2237/334—Etching

Definitions

  • An exemplary embodiment of the present disclosure relates to an etching method and a plasma processing apparatus.
  • Patent Document 1 discloses a method of forming an opening in an organic film by etching the organic film using plasma generated from a process gas.
  • Process gases include etching gases such as oxygen gas, nitrogen gas, or hydrogen gas, and carbonyl sulfide (COS).
  • the present disclosure provides an etching method and a plasma processing apparatus capable of suppressing shape defects of sidewalls of recesses formed by etching.
  • an etching method comprises the steps of (a) providing a substrate comprising an organic film and a mask over the organic film; forming recesses in the organic film by etching the organic film with a first plasma; and (c) after (b), a second plasma generated from a second process gas comprising a tungsten-containing gas. and exposing the recess to.
  • an etching method and plasma processing apparatus capable of suppressing shape defects of sidewalls of recesses formed by etching are provided.
  • FIG. 1 is a schematic diagram of a plasma processing apparatus according to one exemplary embodiment.
  • FIG. 2 is a schematic diagram of a plasma processing apparatus according to one exemplary embodiment.
  • FIG. 3 is a flowchart of an etching method according to one exemplary embodiment.
  • FIG. 4 is a partially enlarged cross-sectional view of an example substrate to which the method of FIG. 3 can be applied.
  • FIG. 5 is a cross-sectional view showing one step of an etching method according to one exemplary embodiment.
  • FIG. 6 is a cross-sectional view showing one step of an etching method according to one exemplary embodiment.
  • FIG. 7 is a cross-sectional view showing one step of an etching method according to one exemplary embodiment.
  • FIG. 8 is a graph showing an example of the relationship between the depth of the recess and the dimension of the recess.
  • the surface of the mask is protected by the tungsten-containing film.
  • the tungsten-containing film acts as a protective film against etching, thus inhibiting etching of the mask by further etching.
  • the surface of the mask includes a top surface of the mask and sidewalls of the mask;
  • active species generated from the fluorine-containing gas in the second plasma etch the deposit, so the deposit is removed.
  • the fluorine-containing gas is at least one selected from the group consisting of hydrofluorocarbon gas, fluorocarbon gas, nitrogen trifluoride ( NF3 ) gas, sulfur hexafluoride ( SF6 ) gas and hydrogen fluoride (HF) gas.
  • the tungsten-containing gas and the reducing gas react in the second plasma to generate tungsten-containing active species. Therefore, a tungsten-containing film is easily formed on the side wall of the recess.
  • the tungsten-containing gas is tungsten hexafluoride (WF 6 ) gas, tungsten hexabromide (WBr 6 ) gas, tungsten hexachloride (WCl 6 ) gas, WF 5 Cl gas and tungsten hexacarbonyl (W(CO) 6 ).
  • the etching method according to any one of [E1] to [E10], containing at least one of gases.
  • a deep recess can be formed while suppressing shape defects of the side wall of the recess.
  • a chamber a substrate support for supporting a substrate within the chamber, the substrate comprising an organic film and a mask on the organic film; a gas supply configured to supply a first process gas including an oxygen-containing gas and a second process gas including a tungsten-containing gas into the chamber; a plasma generator configured to generate a first plasma from the first process gas within the chamber and a second plasma from the second process gas within the chamber; a control unit; with The control unit controls the gas supply unit and the plasma generation unit so that a concave portion is formed in the organic film by etching the organic film with the first plasma, and the concave portion is exposed to the second plasma.
  • a plasma processing apparatus configured to control a
  • FIG. 1 is a diagram for explaining a configuration example of a plasma processing system.
  • a plasma processing system includes a plasma processing apparatus 1 and a controller 2 .
  • the plasma processing system is an example of a substrate processing system
  • the plasma processing apparatus 1 is an example of a substrate processing apparatus.
  • the plasma processing apparatus 1 includes a plasma processing chamber 10 , a substrate support section 11 and a plasma generation section 12 .
  • Plasma processing chamber 10 has a plasma processing space.
  • the plasma processing chamber 10 also has at least one gas inlet for supplying at least one process gas to the plasma processing space and at least one gas outlet for exhausting gas from the plasma processing space.
  • the gas supply port is connected to a gas supply section 20, which will be described later, and the gas discharge port is connected to an exhaust system 40, which will be described later.
  • the substrate support 11 is arranged in the plasma processing space and has a substrate support surface for supporting the substrate.
  • the plasma generator 12 is configured to generate plasma from at least one processing gas supplied within the plasma processing space.
  • Plasma formed in the plasma processing space includes capacitively coupled plasma (CCP), inductively coupled plasma (ICP), ECR plasma (Electron-Cyclotron-resonance plasma), helicon wave excited plasma (HWP). Plasma), surface wave plasma (SWP: Surface Wave Plasma), or the like.
  • Various types of plasma generators may also be used, including AC (Alternating Current) plasma generators and DC (Direct Current) plasma generators.
  • the AC signal (AC power) used in the AC plasma generator has a frequency within the range of 100 kHz to 10 GHz.
  • AC signals include RF (Radio Frequency) signals and microwave signals.
  • the RF signal has a frequency within the range of 100 kHz-150 MHz.
  • the controller 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various steps described in this disclosure. Controller 2 may be configured to control elements of plasma processing apparatus 1 to perform the various processes described herein. In one embodiment, part or all of the controller 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 is implemented by, for example, a computer 2a.
  • Processing unit 2a1 can be configured to perform various control operations by reading a program from storage unit 2a2 and executing the read program. This program may be stored in the storage unit 2a2 in advance, or may be acquired via a medium when necessary.
  • the acquired program is stored in the storage unit 2a2, read from the storage unit 2a2 and executed by the processing unit 2a1.
  • the medium may be various storage media readable by the computer 2a, or may be 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 RAM (Random Access Memory), ROM (Read Only Memory), HDD (Hard Disk Drive), SSD (Solid State Drive), or a combination thereof.
  • the communication interface 2a3 may communicate with the plasma processing apparatus 1 via a communication line such as a LAN (Local Area Network).
  • FIG. 2 is a diagram for explaining a configuration example of an inductively coupled plasma processing apparatus.
  • the inductively coupled plasma processing apparatus 1 includes a plasma processing chamber 10 , a gas supply section 20 , a power supply 30 and an exhaust system 40 .
  • Plasma processing chamber 10 includes dielectric window 101 .
  • the plasma processing apparatus 1 also includes a substrate supporting portion 11 , a gas introduction portion, and an antenna 14 .
  • a substrate support 11 is positioned within the plasma processing chamber 10 .
  • Antenna 14 is positioned on or above plasma processing chamber 10 (ie, on or above dielectric window 101).
  • the plasma processing chamber 10 has a plasma processing space 10 s defined by a dielectric window 101 , sidewalls 102 of the plasma processing chamber 10 and the substrate support 11 .
  • Plasma processing chamber 10 is grounded.
  • the substrate support section 11 includes a body section 111 and a ring assembly 112 .
  • the body portion 111 has a central region 111 a for supporting the substrate W and an annular region 111 b for supporting the ring assembly 112 .
  • a wafer is an example of a substrate W;
  • the annular region 111b of the body portion 111 surrounds the central region 111a of the body portion 111 in plan view.
  • the substrate W is arranged on the central region 111 a of the main body 111
  • the ring assembly 112 is arranged on the annular region 111 b of the main body 111 so as to surround the substrate W on the central region 111 a of the main body 111 .
  • the central region 111a is also referred to as a substrate support surface for supporting the substrate W
  • the annular region 111b is also referred to as a ring support surface for supporting the ring assembly 112.
  • the body portion 111 includes a base 1110 and an electrostatic chuck 1111 .
  • Base 1110 includes a conductive member.
  • the conductive members of base 1110 can function as bias electrodes.
  • An electrostatic chuck 1111 is arranged on the base 1110 .
  • the electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within the ceramic member 1111a.
  • Ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that another member surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member, may have the annular region 111b.
  • the ring assembly 112 may be placed on the annular electrostatic chuck or the annular insulating member, or may be placed on both the electrostatic chuck 1111 and the annular insulating member.
  • at least one RF/DC electrode coupled to an RF power source 31 and/or a DC power source 32, described below, may be disposed within the ceramic member 1111a.
  • at least one RF/DC electrode functions as a bias electrode.
  • the conductive member of the base 1110 and at least one RF/DC electrode may function as a plurality of bias electrodes.
  • the electrostatic electrode 1111b may function as a bias electrode. Accordingly, substrate support 11 includes at least one bias electrode.
  • Ring assembly 112 includes one or more annular members.
  • the one or more annular members include one or more edge rings and at least one cover ring.
  • the edge ring is made of a conductive material or an insulating material
  • the cover ring is made of an insulating material.
  • the substrate supporter 11 may include a temperature control 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 control module may include heaters, heat transfer media, channels 1110a, or combinations thereof.
  • channels 1110 a are formed in base 1110 and one or more heaters are positioned in ceramic member 1111 a of electrostatic chuck 1111 .
  • the substrate support 11 may also include a heat transfer gas supply configured to supply a heat transfer gas to the gap between the back surface of the substrate W and the central region 111a.
  • the gas introduction section is configured to introduce at least one processing gas from the gas supply section 20 into the plasma processing space 10s.
  • the gas inlet includes a Center Gas Injector (CGI) 13 .
  • the central gas injection part 13 is arranged above the substrate support part 11 and attached to a central opening formed in the dielectric window 101 .
  • the central gas injection part 13 has at least one gas supply port 13a, at least one gas channel 13b, and at least one gas introduction port 13c.
  • the processing gas supplied to the gas supply port 13a passes through the gas flow path 13b and is introduced into the plasma processing space 10s from the gas introduction port 13c.
  • the gas introduction part includes one or more side gas injection parts (SGI: Side Gas Injector) attached to one or more openings formed in the side wall 102. may include
  • the gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22 .
  • gas supply 20 is configured to supply at least one process gas from a respective gas source 21 via a respective flow controller 22 to the gas introduction.
  • Each flow controller 22 may include, for example, a mass flow controller or a pressure controlled flow controller.
  • gas supply 20 may include at least one flow modulation device for modulating or pulsing the flow rate of at least one process gas.
  • Power supply 30 includes an RF power supply 31 coupled to plasma processing chamber 10 via at least one impedance matching circuit.
  • RF power supply 31 is configured to supply at least one RF signal (RF power) to at least one bias electrode and antenna 14 .
  • RF power RF power
  • the RF power supply 31 can function as at least part of the plasma generator 12 .
  • a bias RF signal to at least one bias electrode, a bias potential is generated in the substrate W, and ions in the formed plasma can be drawn into the substrate W.
  • the RF power supply 31 includes a first RF generator 31a and a second RF generator 31b.
  • the first RF generator 31a is coupled to the antenna 14 via at least one impedance matching circuit and configured to generate a source RF signal (source RF power) for plasma generation.
  • the source RF signal has a frequency within the range of 10 MHz to 150 MHz.
  • the first RF generator 31a may be configured to generate multiple source RF signals having different frequencies. The generated one or more source RF signals are provided to antenna 14 .
  • the second RF generator 31b is coupled to at least one bias 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.
  • the bias RF signal has a frequency lower than the frequency of the source RF signal.
  • the bias RF signal has a frequency within the range of 100 kHz to 60 MHz.
  • the second RF generator 31b may be configured to generate multiple bias RF signals having different frequencies.
  • One or more bias RF signals generated are provided to at least one bias electrode.
  • at least one of the source RF signal and the bias RF signal may be pulsed.
  • Power supply 30 may also include a DC power supply 32 coupled to plasma processing chamber 10 .
  • the DC power supply 32 includes a bias DC generator 32a.
  • the bias DC generator 32a is connected to at least one bias electrode and configured to generate a bias DC signal.
  • the generated bias DC signal is applied to at least one bias electrode.
  • the bias DC signal may be pulsed.
  • a sequence of voltage pulses is applied to at least one bias electrode.
  • the voltage pulses may have rectangular, trapezoidal, triangular, or combinations thereof pulse waveforms.
  • a waveform generator for generating a sequence of voltage pulses from the DC signal is connected between the bias DC generator 32a and the at least one bias electrode. Therefore, the bias DC generator 32a and the waveform generator constitute a voltage pulse generator.
  • the voltage pulse may have a positive polarity or a negative polarity.
  • the sequence of voltage pulses may include one or more positive voltage pulses and one or more negative voltage pulses in one cycle.
  • the bias DC generator 32a may be provided in addition to the RF power supply 31, or may be provided instead of the second RF generator 31b.
  • the antenna 14 includes one or more coils.
  • antenna 14 may include an outer coil and an inner coil that are coaxially arranged.
  • the RF power supply 31 may be connected to both the outer coil and the inner coil, or may be connected to either one of the outer coil and the inner coil.
  • the same RF generator may be connected to both the outer and inner coils, or separate RF generators may be separately connected to the outer and inner coils.
  • the exhaust system 40 may be connected to a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10, for example.
  • 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.
  • Vacuum pumps may include turbomolecular pumps, dry pumps, or combinations thereof.
  • FIG. 3 is a flowchart of an etching method according to one exemplary embodiment.
  • An etching method MT (hereinafter referred to as "method MT") shown in FIG. 3 can be performed by the plasma processing apparatus 1 of the above embodiment.
  • the method MT may be applied to the substrate W.
  • FIG. 4 is a partially enlarged cross-sectional view of an example substrate to which the method of FIG. 3 can be applied.
  • the substrate W comprises an organic film (carbon-containing film) SF and a mask MK over the organic film SF.
  • the substrate W may comprise an underlayer UR.
  • An organic film SF is provided on the base film UR.
  • the organic film SF may be an amorphous carbon film or a spin-on carbon film (SOC film: Spin On Carbon film).
  • the mask MK may have an opening OP.
  • the opening OP may be a hole or trench.
  • the mask MK may contain silicon.
  • Mask MK may be a silicon-containing film.
  • the silicon-containing film may include at least one of silicon oxide, silicon nitride and silicon oxynitride.
  • the base film UR may be a silicon-containing film.
  • the silicon-containing film may include at least one of silicon oxide, silicon nitride and silicon oxynitride.
  • the silicon-containing film may comprise a multilayer film including a silicon oxide film and a silicon nitride film. Silicon oxide films and silicon nitride films may be alternately stacked.
  • the silicon-containing film may be a laminated film including a silicon (Si) film and a silicon germanium (SiGe) film.
  • FIGS. 3 to 7 are cross-sectional views illustrating one step of an etching method according to one exemplary embodiment.
  • the method MT can be performed in the plasma processing apparatus 1 by controlling each unit of the plasma processing apparatus 1 by the control unit 2 .
  • a substrate W on a substrate supporter 11 (substrate supporter) placed in a plasma processing chamber 10 is processed.
  • the method MT can include steps ST1, ST2, ST3, ST4 and ST5. Steps ST1 to ST6 may be performed in order. Method MT may not include at least one of step ST4 and step ST5.
  • step ST1 the substrate W shown in FIG. 4 is provided.
  • a substrate W may be supported by a substrate support 11 within the plasma processing chamber 10 .
  • step ST2 the organic film SF is etched by a first plasma P1 generated from a first processing gas containing an oxygen-containing gas, thereby forming a recess RS in the organic film SF.
  • the recess RS may have sidewalls RSa and a bottom RSb.
  • Process ST2 may be performed as follows. First, the gas supply unit 20 supplies the first processing gas into the plasma processing chamber 10 . Next, the plasma generator 12 generates the first plasma P1 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 recess RS is formed in the organic film SF by etching the organic film SF with the first plasma P1.
  • oxygen-containing gases include oxygen ( O2 ) gas, carbon monoxide (CO) gas and carbon dioxide ( CO2 ) gas.
  • the first process gas may contain a sulfur-containing gas.
  • sulfur-containing gases include carbonyl sulfide (COS) and sulfur dioxide ( SO2 ) gases.
  • the first process gas may be metal-free.
  • the first process gas may be free of tungsten, molybdenum and titanium.
  • step ST2 can be set so that the opening OP is not clogged with deposits adhering to the opening OP.
  • the deposit may contain the same material contained in the mask MK.
  • step ST3 the recesses RS are exposed to the second plasma P2 generated from the second processing gas containing tungsten-containing gas or metal halide gas.
  • the sidewall RSa and bottom RSb of the recess RS may be exposed to the second plasma P2.
  • Process ST3 may be performed as follows. First, the gas supply unit 20 supplies the second processing gas into the plasma processing chamber 10 . Next, the plasma generator 12 generates the second plasma P2 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 recess RS is exposed to the second plasma P2.
  • a tungsten-containing film WF may be formed on the sidewall RSa of the recess RS.
  • the tungsten-containing film WF may be formed on the surface of the mask MK.
  • the surface of the mask MK includes the upper surface of the mask MK and sidewalls of the opening OP.
  • the thickness of the tungsten-containing film WF on the upper surface of the mask MK may be greater than the thickness of the tungsten-containing film WF on the side walls of the opening OP.
  • Tungsten-containing film WF may not be formed on bottom RSb of recess RS, and may not be formed on part of sidewall RSa adjacent to bottom RSb.
  • the tungsten-containing film WF may be a tungsten film.
  • a tungsten-containing gas may include a tungsten halide gas.
  • tungsten halide gases include tungsten hexafluoride (WF 6 ) gas, tungsten hexabromide (WBr 6 ) gas, tungsten hexachloride (WCl 6 ) gas and WF 5 Cl gas.
  • the tungsten-containing gas may include hexacarbonyl tungsten (W(CO) 6 ) gas.
  • metal halide gases include tungsten halide gases, molybdenum halide gases and titanium halide gases.
  • the second process gas contains a molybdenum halide gas
  • a molybdenum-containing film can be formed instead of the tungsten-containing film WF.
  • the second process gas contains titanium halide
  • a titanium-containing film can be formed instead of the tungsten-containing film WF.
  • the second process gas is different than the first process gas.
  • the second process gas may not contain oxygen.
  • the second process gas may contain a fluorine-containing gas.
  • the fluorine-containing gas removes deposits adhering to the opening OP of the mask MK in step ST2.
  • fluorine-containing gases include hydrofluorocarbon gases, fluorocarbon (eg CF4 ) gases, NF3 gases, SF6 gases and HF gases.
  • the second process gas may contain a reducing gas that reduces the tungsten-containing gas.
  • the reducing gas may be a hydrogen-containing gas or a halogen-containing gas.
  • hydrogen-containing gases include hydrogen ( H2 ) gas and silane ( SiH4 ) gas.
  • halogen-containing gases include silicon tetrachloride ( SiCl4 ) gas and silicon tetrafluoride ( SiF4 ) gas.
  • the second processing gas may contain an inert gas.
  • inert gases include noble gases.
  • noble gases include helium gas, neon gas, argon gas, krypton gas and xenon gas.
  • the flow rate of the tungsten-containing gas may be the lowest among all the gases contained in the second processing gas excluding the inert gas.
  • the flow rate of the tungsten-containing gas may be less than the flow rate of the fluorine-containing gas or may be less than the flow rate of the reducing gas.
  • the flow rate of the fluorine-containing gas may be less than the flow rate of the reducing gas.
  • the ratio of the flow rate of the tungsten-containing gas to the total flow rate of the second processing gas excluding the inert gas may be less than 1% by volume, or may be 0.5% by volume or less.
  • the duration of step ST3 may be shorter than the duration of step ST2, or may be 1/50 or less of the duration of step ST2.
  • the process ST3 may be performed in the same plasma processing chamber as the plasma processing chamber 10 in which the process ST2 is performed, or may be performed in a plasma processing chamber different from the plasma processing chamber 10 in which the process ST2 is performed.
  • step ST4 as shown in FIG. 7, the organic film SF is etched by the first plasma P1. According to step ST4, the bottom RSb of the recess RS is etched, so the recess RS becomes deeper. The tungsten-containing film WF can be removed by step ST4.
  • step ST5 steps ST3 and ST4 are repeated.
  • the steps ST3 and ST4 may be repeated until the bottom RSb of the recess RS reaches the base film UR.
  • the above method MT it is possible to suppress the shape defect (bowing) of the sidewall RSa of the recess RS formed by etching.
  • the mechanism by which shape defects are suppressed is presumed as follows, but is not limited to this. Active species generated from the tungsten-containing gas or the metal halide gas in the second plasma P2 adhere to the sidewall RSa of the recess RS. Thereby, a tungsten-containing film WF or a metal-containing film is formed on the sidewall RSa of the recess RS.
  • etching of the sidewall RSa of the recess RS by further etching is suppressed. Therefore, the shape defect of the side wall RSa of the recess RS is suppressed.
  • the following mechanism is also conceivable. Active species generated from the tungsten-containing gas or the metal halide gas react with the sidewall RSa of the recess RS in the second plasma P2. Thereby, the sidewall RSa of the recess RS is modified to form a modified region. Since the modified region functions as a protective region against etching, further etching of the side wall RSa of the recess RS is suppressed. Therefore, the shape defect of the side wall RSa of the recess RS is suppressed.
  • the tungsten-containing film WF When the tungsten-containing film WF is formed on the surface of the mask MK in step ST3, the surface of the mask MK is protected by the tungsten-containing film WF. Since the tungsten-containing film WF functions as a protective film against etching, etching of the mask MK in step ST4 is suppressed. Therefore, the etching selectivity of the organic film SF with respect to the mask MK can be increased.
  • step ST3 deposits adhering to the opening OP of the mask MK in step ST2 can be removed.
  • active species generated from the fluorine-containing gas in the second plasma P2 etch the deposit, so the deposit is removed.
  • the tungsten-containing gas reacts with the reducing gas to generate tungsten-containing active species in the second plasma P2. Therefore, the tungsten-containing film WF is easily formed on the sidewall RSa of the recess RS.
  • the second process gas includes WF6 gas and H2 gas
  • the chemical reaction may produce tungsten (W) and hydrogen fluoride (HF).
  • W tungsten
  • HF hydrogen fluoride
  • Tungsten may form a tungsten-containing film WF.
  • Hydrogen fluoride can contribute to the removal of deposits adhering to the opening OP.
  • the flow rate of the tungsten-containing gas is the lowest among all the gases contained in the second processing gas excluding the inert gas, the amount of the tungsten-containing film WF formed on the surface of the mask MK in step ST3 is small. Therefore, blockage of the opening OP of the mask MK can be suppressed in step ST3.
  • the ratio of the flow rate of the tungsten-containing gas to the total flow rate of the second processing gas excluding the inert gas is 1% by volume or less, the amount of the tungsten-containing film WF formed on the surface of the mask MK in step ST3 is reduced. . Therefore, blockage of the opening OP of the mask MK can be suppressed in step ST3. In this case, since the number of active species in the first plasma P1 supplied into the recess RS increases, the etching rate in step ST4 increases.
  • the method MT includes the step ST4, etching of the sidewall RSa of the recess RS is suppressed in the step ST4.
  • the deep recess RS can be formed while suppressing the shape defect of the side wall RSa of the recess RS.
  • step ST3 When the duration of step ST3 is shorter than the duration of step ST2, the amount of tungsten-containing film WF formed on the surface of mask MK in step ST3 is reduced. Therefore, blockage of the opening OP of the mask MK can be suppressed in step ST3.
  • step ST2 When the first processing gas contains a sulfur-containing gas, etching of the sidewall RSa of the recess RS is suppressed in step ST2.
  • a substrate including an amorphous carbon film and a mask on the amorphous carbon film was prepared (step ST1).
  • the mask is a silicon oxynitride film with openings.
  • the first process gas includes O2 gas and COS gas.
  • the second process gas includes NF3 gas, H2 gas, WF6 gas, and Ar gas.
  • the flow rate of WF6 gas was the lowest among all the gases contained in the second process gas except the inert gas. That is, the flow rate of WF6 gas was less than that of NF3 gas and less than that of H2 gas.
  • the ratio of the flow rate of WF6 gas to the total flow rate of the second process gas excluding inert gas was 0.5% by volume.
  • the total flow rate of the second process gas excluding the inert gas is the sum of the flow rate of WF6 gas, the flow rate of NF3 gas, and the flow rate of H2 gas.
  • the duration of step ST3 was shorter than the duration of step ST2.
  • step ST1 the amorphous carbon film was etched with the first plasma (step ST4).
  • process ST3 and process ST4 were repeated (process ST5).
  • Steps ST1 to ST5 were performed by the plasma processing apparatus 1.
  • the second process gas of the third experiment includes NF3 gas, H2 gas and Ar gas.
  • FIG. 8 is a graph showing an example of the relationship between the depth of the recess and the dimensions of the recess.
  • the dimension of the recess is measured in a direction orthogonal to the depth direction of the recess.
  • profile E1 shows the depth and dimensions of the recess in the first experiment.
  • Profile E2 shows the depth and dimensions of the recess in the second experiment.
  • Profile E3 shows the depth and dimensions of the recess in the third experiment.
  • the dimensions of the recesses in the first and second experiments are significantly smaller than the dimensions of the recesses in the third experiment. Therefore, it can be seen that in the first experiment and the second experiment, the shape defect (bowing) of the side wall of the recess was suppressed as compared with the third experiment.
  • the shape defect (bowing) of the side wall of the recess was suppressed compared to the third experiment.
  • the etching rate of the fourth experiment was smaller than the etching rates of the first to third experiments.
  • the tungsten film formed on the surface of the mask in step ST3 is thick, it is considered that the etching rate is relatively low.
  • SYMBOLS 1 Plasma processing apparatus, 2... Control part, 10... Plasma process chamber, 11... Substrate support part, 12... Plasma generation part, 20... Gas supply part, MK... Mask, P1... First plasma, P2... Second plasma , RS... concave portion, SF... organic film, W... substrate.

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  • Drying Of Semiconductors (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
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