WO2023162161A1 - 温調システム、温調方法、基板処理方法及び基板処理装置 - Google Patents

温調システム、温調方法、基板処理方法及び基板処理装置 Download PDF

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Publication number
WO2023162161A1
WO2023162161A1 PCT/JP2022/007982 JP2022007982W WO2023162161A1 WO 2023162161 A1 WO2023162161 A1 WO 2023162161A1 JP 2022007982 W JP2022007982 W JP 2022007982W WO 2023162161 A1 WO2023162161 A1 WO 2023162161A1
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WO
WIPO (PCT)
Prior art keywords
temperature control
gas
temperature
substrate
control unit
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/007982
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English (en)
French (fr)
Japanese (ja)
Inventor
雅彦 横井
康基 田中
幕樹 戸村
嘉英 木原
正浩 米倉
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Tokyo Electron Ltd
Nippon Sanso Holdings Corp
Original Assignee
Tokyo Electron Ltd
Nippon Sanso Holdings Corp
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Application filed by Tokyo Electron Ltd, Nippon Sanso Holdings Corp filed Critical Tokyo Electron Ltd
Priority to JP2024502392A priority Critical patent/JPWO2023162161A1/ja
Priority to KR1020247028191A priority patent/KR20240153992A/ko
Priority to PCT/JP2022/007982 priority patent/WO2023162161A1/ja
Priority to TW112106708A priority patent/TW202414572A/zh
Publication of WO2023162161A1 publication Critical patent/WO2023162161A1/ja
Priority to US18/810,862 priority patent/US20240412955A1/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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0431—Apparatus for thermal treatment
    • H10P72/0434—Apparatus for thermal treatment mainly by convection
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D3/00—Devices using other cold materials; Devices using cold-storage bodies
    • F25D3/10—Devices using other cold materials; Devices using cold-storage bodies using liquefied gases, e.g. liquid air
    • 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
    • H01J37/32458—Vessel
    • H01J37/32522—Temperature
    • 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
    • H01J37/32715—Workpiece holder
    • H01J37/32724—Temperature
    • 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
    • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
    • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
    • H10P50/282—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials
    • H10P50/283—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials by chemical means
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/76—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using mechanical means, e.g. clamps or pinches
    • H10P72/7604—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using mechanical means, e.g. clamps or pinches the wafers being placed on a susceptor, stage or support
    • 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
    • H01J2237/002—Cooling arrangements
    • 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
    • H01J2237/20—Positioning, supporting, modifying or maintaining the physical state of objects being observed or treated
    • H01J2237/2001—Maintaining constant desired temperature
    • 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

  • the present disclosure relates to a temperature control system, a temperature control method, a substrate processing method, and a substrate processing apparatus.
  • the temperature is controlled by a chiller that circulates the temperature control medium through the flow path in the mounting table using a pump.
  • a chiller that circulates the temperature control medium through the flow path in the mounting table using a pump.
  • it is proposed to circulate a temperature control medium cooled by a chiller in a flow path in the mounting table and control the temperature of the wafer via a heat transfer gas flowing between the mounting table and the wafer.
  • the present disclosure provides a temperature control system, a temperature control method, a substrate processing method, and a substrate processing apparatus that can be used in low-temperature regions.
  • a temperature control system is a temperature control system that cools members in a plasma processing chamber, and includes a condenser that condenses and liquefies a temperature control medium that is in a gaseous state at normal temperature and normal pressure, and a condenser that condenses.
  • a heat exchanger that cools a liquefied temperature control medium
  • a temperature control unit that cools a member by heat exchange with the temperature control medium cooled by the heat exchanger
  • a pump that circulates the temperature control medium.
  • FIG. 1 is a diagram showing an example of a plasma processing system according to the first embodiment of the present disclosure.
  • FIG. 2 is a diagram showing an example of a temperature control system according to the first embodiment.
  • FIG. 3 is a graph showing an example of viscosity characteristics of each temperature control medium.
  • FIG. 4 is a graph showing an example of vapor pressure characteristics of each temperature control medium.
  • FIG. 5 is a flowchart showing an example of temperature control processing in the first embodiment.
  • FIG. 6 is a flow chart showing an example of substrate processing in the second embodiment.
  • FIG. 7 is a partially enlarged cross-sectional view showing an example of the substrate provided in the second embodiment.
  • FIG. 8 is a partially enlarged cross-sectional view showing an example of the substrate after performing the substrate processing method shown in FIG. FIG.
  • FIG. 9 is an example of a timing chart regarding the substrate processing method according to the second embodiment.
  • FIG. 10 is a flowchart showing an example of substrate processing in the third embodiment.
  • FIG. 11 is a partially enlarged cross-sectional view showing an example of the substrate provided in the third embodiment.
  • FIG. 12(a) is a partially enlarged cross-sectional view of an example substrate to which the substrate processing method shown in FIG. 10 is applied, and
  • FIG. FIG. 4 is an enlarged partial cross-sectional view of an example substrate that has been etched.
  • FIG. 13 is an example of a timing chart regarding the substrate processing method according to the third embodiment.
  • the temperature control medium may dry out due to the heat input from the plasma.
  • the liquid-phase temperature control medium accumulates in the lower part of the channel in the temperature control part, and the upper part becomes the gas phase.
  • the vapor pressure of the temperature control medium is required to be sufficiently low. Therefore, there is a demand for a temperature control medium having a sufficiently low vapor pressure in consideration of the temperature rise of the temperature control medium due to the heat input from the plasma.
  • the temperature control system is expected to be used in low temperature regions.
  • FIG. 1 is a diagram showing an example of a plasma processing system according to the first embodiment of the present disclosure.
  • the plasma processing system includes a capacitively coupled plasma processing apparatus 1 and a controller 2 .
  • a capacitively 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 .
  • the plasma processing apparatus 1 includes a substrate support section 11 and a gas introduction section.
  • the gas introduction is configured to introduce at least one process gas into the plasma processing chamber 10 .
  • the gas introduction section includes a showerhead 13 .
  • a substrate support 11 is positioned within the plasma processing chamber 10 .
  • the showerhead 13 is arranged above the substrate support 11 .
  • showerhead 13 forms at least a portion of the ceiling of plasma processing chamber 10 .
  • the plasma processing chamber 10 has a plasma processing space 10 s defined by a showerhead 13 , side walls 10 a of the plasma processing chamber 10 and a substrate support 11 .
  • the plasma processing chamber 10 has at least one gas supply port for supplying at least one processing gas to the plasma processing space 10s and at least one gas exhaust port for exhausting gas from the plasma processing space 10s.
  • Plasma processing chamber 10 is grounded.
  • the showerhead 13 and substrate support 11 are electrically insulated from the housing of the plasma processing chamber 10 .
  • 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.
  • a conductive member of the base 1110 can function as a bottom electrode.
  • 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 (Radio Frequency) power supply 31 and/or a DC (Direct Current) power supply 32, which will be described later, may be arranged in the ceramic member 1111a.
  • at least one RF/DC electrode functions as the bottom electrode. If a bias RF signal and/or a DC signal, described below, is applied to at least one RF/DC electrode, the RF/DC electrode is also called a bias electrode.
  • the conductive member of the base 1110 and at least one RF/DC electrode may function as a plurality of lower electrodes.
  • the electrostatic electrode 1111b may function as a lower electrode. Accordingly, the substrate support 11 includes at least one bottom 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 flow path 1110a is connected to a temperature control system 50, which will be described later, via pipes 51a and 51b, and is supplied with a temperature control medium.
  • 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 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 introduction ports 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 through a plurality of gas introduction ports 13c.
  • showerhead 13 also includes at least one upper electrode.
  • the gas introduction part may include one or more side gas injectors (SGI: Side Gas Injector) attached to one or more openings formed in the side wall 10a.
  • SGI Side Gas Injector
  • 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 respective gas sources 21 through respective flow controllers 22 to showerhead 13 .
  • Each flow controller 22 may include, for example, a mass flow controller or a pressure controlled flow controller.
  • gas supply 20 may include one or more flow modulation devices that modulate or pulse the flow 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 lower electrode and/or at least one upper electrode.
  • RF power source 31 may function as at least part of a plasma generator configured to generate a plasma from one or more process gases in plasma processing chamber 10 .
  • a bias potential is generated in the substrate W, and ion components 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 at least one lower electrode and/or at least one upper electrode via at least one impedance matching circuit 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.
  • One or more source RF signals generated are provided to at least one bottom electrode and/or at least one top electrode.
  • the second RF generator 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.
  • 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 bottom electrode. Also, in various embodiments, 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 first DC generator 32a and a second DC generator 32b.
  • the first DC generator 32a is connected to the at least one bottom electrode and configured to generate a first DC signal.
  • a generated first bias DC signal is applied to at least one bottom electrode.
  • the second DC generator 32b is connected to the at least one top electrode and configured to generate a second DC signal. The generated second DC signal is applied to at least one top electrode.
  • At least one of the first and second DC signals may be pulsed.
  • a sequence of voltage pulses is applied to at least one bottom electrode and/or at least one top 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 a DC signal is connected between the first DC generator 32a and the at least one bottom electrode. Therefore, the first DC generator 32a and the waveform generator constitute a voltage pulse generator.
  • the voltage pulse generator is connected to at least one upper electrode.
  • the voltage pulse may have a positive polarity or a negative polarity.
  • the sequence of voltage pulses may include one or more positive voltage pulses and one or more negative voltage pulses in one cycle.
  • the first and second DC generators 32a and 32b may be provided in addition to the RF power supply 31, and the first DC generator 32a may be provided instead of the second RF generator 31b. good.
  • 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.
  • the temperature control system 50 supplies a temperature control medium to the flow path 1110a of the base 1110 through the pipes 51a and 51b, and the substrate W placed on the central region 111a of the main body 111 reaches a target temperature (predetermined temperature).
  • a target temperature may be the temperature of the electrostatic chuck 1111, the ring assembly 112, or the like.
  • the temperature control system 50 controls the temperature control medium flowing through the flow path 1110a, a heater (not shown), etc., so that the substrate W is at a predetermined temperature, eg, -70.degree.
  • 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 showing an example of a temperature control system according to the first embodiment.
  • the temperature control system 50 has a gas supply section 52 , a condenser 53 , a cooling jacket 54 , a pump 55 and a heat exchanger 56 .
  • the temperature control system 50 also has a control section 60 that controls each section from the gas supply section 52 to the heat exchanger 56 according to instructions from the control section 2 .
  • the gas supply unit 52 supplies the condenser 53 with a temperature control medium that is in a gaseous state at normal temperature and normal pressure.
  • the gas supply unit 52 supplies gases such as C3F8 and C3H2F4 to the condenser 53 as temperature control media.
  • the condenser 53 condenses and liquefies the gaseous temperature control medium supplied from the gas supply unit 52 .
  • the condenser 53 is, for example, an airtight tank, and the temperature control medium inside the condenser 53 is liquefied by cooling the condenser 53 with the cooling jacket 54 .
  • the temperature control medium is liquefied at a temperature higher than the boiling point at the atmospheric pressure.
  • the pressure in the condenser 53 may be the atmospheric pressure if the performance of the cooling jacket 54 is such that it can cool the temperature control medium to the boiling point or lower even at the atmospheric pressure.
  • the pump 55 circulates the liquid-phase temperature control medium liquefied in the condenser 53 to the heat exchanger 56 and the flow path 1110 a of the base 1110 .
  • the pump 55 can set the flow rate when circulating the temperature control medium to, for example, 15 L/min or more.
  • the heat exchanger 56 cools the liquid phase temperature control medium liquefied by the condenser 53 .
  • the heat exchanger 56 cools the temperature control medium to a predetermined temperature using a refrigerant such as liquid nitrogen or liquid helium.
  • the predetermined temperature can be, for example, a temperature in the range of -50°C to -150°C.
  • a coolant is supplied to the heat exchanger 56 through a pipe 57 from a coolant supply source (not shown).
  • the heat exchanger 56 cools the temperature control medium, which flows from the pipe 51f on the pump 55 side, to a predetermined temperature with the refrigerant and supplies the cooled medium to the pipe 51a.
  • the pipe 51 a is a pipe on the side from which the temperature control medium flows out from the temperature control system 50 and is connected to the outlet side of the heat exchanger 56 .
  • the pipe 51b is a pipe on the side into which the temperature control medium flows into the temperature control system 50, and branches within the temperature control system 50 into pipes 51c and 51d.
  • the pipe 51c is a pipe for circulating the liquid temperature control medium among the temperature control medium flowing in the pipe 51b to the pump 55 .
  • the pipe 51 d is connected to the upper part of the condenser 53 , and is a pipe for returning vaporized gas (the temperature control medium in gas phase) of the temperature control medium flowing in the pipe 51 b to the upper part of the condenser 53 .
  • the pipe 51 f is connected to the heat exchanger 56 via the pump 55 . That is, the liquid-phase temperature control medium circulates through the flow path composed of the pipe 51a, the flow channel 1110a, the pipe 51b, the pipe 51c, the pipe 51f, the pump 55, and the heat exchanger .
  • the pressure of the circulating liquid-phase temperature control medium is higher than the atmospheric pressure.
  • the temperature control medium is first condensed and liquefied by the condenser 53 and supplied to the pipe 51f through the pipe 51e.
  • the liquid-phase temperature control medium in the pipe 51 f is sent to the heat exchanger 56 by the pump 55 .
  • a liquid-phase temperature control medium is supplied from the heat exchanger 56 to the flow path 1110a through the pipe 51a, as indicated by an arrow 58a.
  • the base 1110 is cooled by heat exchange with the temperature control medium. Further, by cooling the base 1110, the electrostatic chuck 1111 is cooled, and the substrate W placed on the central region 111a of the electrostatic chuck 1111 is cooled.
  • the temperature control medium may contain a gas phase due to heat exchange in the flow path 1110a.
  • the temperature control medium after heat exchange is allowed to contain a gas phase in the flow path 1110a inside the base 1110 .
  • the base 1110 is an example of a temperature control unit that cools the members (the electrostatic chuck 1111 and the substrate W) by heat exchange with a temperature control medium cooled by the heat exchanger 56 .
  • the temperature of the substrate W which is subject to temperature control, will be considered.
  • Heat is input to the substrate W from the plasma, and heat is emitted to the temperature control medium via the electrostatic chuck 1111 and the base 1110 .
  • heat release is proportional to the flow rate of the temperature control medium and the temperature difference, so the temperature of the substrate W is inversely proportional to the flow rate of the temperature control medium.
  • the RF power for generating plasma is 2 kW and the flow rate of the temperature control medium is 3 m 3 /h
  • the temperature of the substrate W can be obtained as -92°C.
  • the temperature control medium (C3F8 or C3H2F4) of the present embodiment can increase the temperature of the substrate W by increasing the flow rate of the temperature control medium even if the RF power for generating plasma is 1 kW or more. It can be below a predetermined temperature (eg, -50°C). Further, since the temperature control medium (C3F8 or C3H2F4) of the present embodiment has a sufficiently low vapor pressure as described later, it is possible to suppress deterioration in cooling performance due to dryout.
  • the temperature control medium flows out from the flow path 1110a to the pipe 51b as indicated by the arrow 58b.
  • the liquid-phase temperature control medium flows into the pump 55 via the pipes 51c and 51f as indicated by an arrow 58c.
  • a liquid-phase temperature control medium corresponding to the amount reduced by vaporization is supplied from the condenser 53 through the pipe 51e.
  • the vapor phase temperature control medium is returned to the upper portion of the condenser 53 via the pipe 51d.
  • the temperature control medium circulates between the temperature control system 50 and the base 1110 by repeating such a cycle.
  • FIG. 3 is a graph showing an example of viscosity characteristics of each temperature control medium.
  • a graph 200 shown in FIG. 3 is a graph in which the vertical axis represents the viscosity (mPa ⁇ sec) of each temperature control medium and the horizontal axis represents the temperature (° C.).
  • Graph 201 is a graph showing the viscosity of C3F8.
  • Graph 202 is a graph showing the viscosity of C3H2F4 (R1234yf).
  • a graph 203 is a graph showing the viscosity of conventional common brine.
  • a line 204 represents the upper limit value (6 mPa ⁇ sec) of viscosity when used as a refrigerant.
  • a line 205 is a line representing ⁇ 70° C. as an example of the temperature used as the refrigerant.
  • a region 206 is defined by the predetermined temperature range used as the coolant and the upper limit of the viscosity.
  • the predetermined temperature range used as the coolant is -50°C to -150°C, it is required that the graph be within region 206 in this temperature range. Since the graphs 201 and 202 are located within the region 206 in the predetermined temperature range, it can be seen that C3F8 and C3H2F4 are suitable as temperature control media. On the other hand, the graph 203 shows that a portion of the brine passes through the region 206 within a predetermined temperature range, but is outside the region 206 at a temperature of ⁇ 70° C. or lower, and the viscosity does not satisfy the conditions. It can be seen that this embodiment is not suitable as a temperature control medium.
  • FIG. 4 is a graph showing an example of vapor pressure characteristics of each temperature control medium.
  • a graph 210 shown in FIG. 4 is a graph in which the vertical axis represents the vapor pressure (Pa) of each temperature control medium, and the horizontal axis represents the temperature (° C.).
  • Graph 211 is a graph showing the vapor pressure of C3F8.
  • Graph 212 is a graph showing the vapor pressure of C3H2F4 (R1234yf).
  • a graph 213 is a graph showing the vapor pressure of conventional general brine.
  • a line 214 represents the lower limit of vapor pressure (standard atmospheric pressure: 1013.25 hPa) when used as a refrigerant.
  • a region 215 is a region defined by a predetermined temperature range used as a refrigerant and a lower limit value of vapor pressure.
  • the predetermined temperature range used as the refrigerant is -50°C to -150°C, it is required that the region 215 be included in the liquid phase range within this temperature range.
  • Graphs 211 and 212 show that C3F8 and C3H2F4 are suitable as a temperature control medium because region 215 is included in the liquid phase range within a predetermined temperature range. That is, C3F8 and C3H2F4 are liquid phases at a predetermined temperature and in an equilibrium state above atmospheric pressure.
  • the temperature control medium may contain a gas phase in a non-equilibrium state in which it flows as a fluid during circulation.
  • the conventional common brine since the region 215 is included in the range of the liquid phase in the predetermined temperature range, the conventional common brine also satisfies the conditions of the temperature control medium in terms of vapor pressure. That is, as can be seen from graphs 200 and 210 in FIGS. 3 and 4, C3F8 and C3H2F4 are suitable as temperature control media under both viscosity and vapor pressure conditions. That is, by using a temperature control medium that is positioned within the region 206 of the graph 200 and whose liquid phase is included in the region 215 of the graph 210, it is possible to suppress an increase in the viscosity of the temperature control medium in the operating temperature range.
  • C3F8 and C3H2F4 are temperature control media having a sufficiently low vapor pressure in consideration of the temperature rise of the temperature control medium due to heat input from the plasma.
  • the temperature control medium is not limited to C3F8 and C3H2F4 as long as its viscosity and vapor pressure are within the region 206 of the graph 200 and the region 215 of the graph 210 is included in the range of the liquid phase, Other substances may be used.
  • FIG. 5 is a flowchart showing an example of temperature control processing in the first embodiment.
  • the gas supply unit 52 supplies the condenser 53 with normal temperature and normal pressure. , the supply of the temperature control medium in gaseous state is started.
  • the controller 60 causes the temperature control medium in the gaseous state to condense and liquefy in the condenser 53 (step S1).
  • the control unit 60 operates the pump 55 to circulate the temperature control medium to the heat exchanger 56 and cool the temperature control medium in the heat exchanger 56 (step S2).
  • the control unit 60 supplies the temperature control medium cooled by the heat exchanger 56 to the base 1110, which is a temperature control unit that cools the members (the electrostatic chuck 1111 and the substrate W) (step S3).
  • the control unit 60 cools the members on the base 1110 with the temperature control medium (step S4), and controls the temperature control medium to return to the condenser 53 after heat exchange (step S4). step S5).
  • the control unit 60 determines whether an instruction to end the temperature control process has been issued from the control unit 2, that is, whether to end the temperature control process (step S6). When the controller 60 determines not to end the temperature control process (step S6: No), the process returns to step S1. On the other hand, when the controller 60 determines to end the temperature control process (step S6: Yes), the control part 60 ends the temperature control process.
  • FIG. 6 is a flow chart showing an example of substrate processing in the second embodiment.
  • the substrate processing method illustrated in FIG. 6 is performed to etch a film containing silicon.
  • This substrate processing method can be used, for example, in manufacturing a NAND flash memory having a three-dimensional structure.
  • the substrate processing method is performed using a plasma processing system.
  • the control unit 2 controls the plasma processing apparatus 1 so that the substrate W1 is provided in the plasma processing chamber 10 (step S11). A substrate W1 is placed on and held by the electrostatic chuck 1111 .
  • FIG. 7 is a partially enlarged cross-sectional view showing an example of the substrate provided in the second embodiment.
  • the substrate W1 shown in FIG. 7 has an underlayer UL, a film SF1 and a mask MSK.
  • the underlayer UL may be a layer made of polysilicon.
  • the film SF1 is provided on the underlying layer UL.
  • Film SF1 contains silicon.
  • the film SF1 may be a laminated film including one or more silicon oxide films and one or more silicon nitride films.
  • the film SF1 is a multilayer film including multiple silicon oxide films IL1 and multiple silicon nitride films IL2.
  • the plurality of silicon oxide films IL1 and the plurality of silicon nitride films IL2 are alternately laminated.
  • the film SF1 may be another single layer film containing silicon or another multilayer film containing silicon.
  • the film SF1 can be, for example, a low dielectric constant film made of SiOC, SiOF, SiCOH, or the like, or a polysilicon film.
  • the film SF1 can be a laminated film including one or more silicon oxide films and one or more polysilicon films, for example.
  • the mask MSK is provided on the film SF1.
  • the mask MSK has a pattern for forming spaces such as holes in the film SF1.
  • Mask MSK may be, for example, a hard mask.
  • Mask MSK can be, for example, a carbon-containing mask and/or a metal-containing mask.
  • the carbon-containing mask is made of, for example, at least one selected from the group consisting of spin-on carbon, tungsten carbide, amorphous carbon, and boron carbide.
  • the metal-containing mask is formed from at least one selected from the group consisting of titanium nitride, titanium oxide, and tungsten.
  • mask MSK may be a boron-containing mask formed from, for example, silicon boride, boron nitride, or boron carbide.
  • the control unit 2 controls the temperature control system 50 and starts temperature control processing so that the temperature of the substrate supporting unit 11 (electrostatic chuck 1111, substrate W1) reaches a predetermined temperature (step S12). That is, the control unit 2 instructs the control unit 60 of the temperature control system 50 to execute the temperature control process of the first embodiment. Note that the temperature control process is the same as that of the first embodiment, so the description thereof will be omitted.
  • the control unit 2 controls the plasma processing apparatus 1 so as to execute the step of etching the substrate W1 when the temperature of the substrate W1 reaches a predetermined temperature by the temperature control process (step S13).
  • a plasma is generated from the first process gas within the plasma processing chamber 10 .
  • chemical species from this plasma etch the film SF1.
  • the first processing gas used in step S13 contains hydrogen fluoride gas.
  • the flow rate of the hydrogen fluoride gas is greater than the flow rates of the other gases contained in the first processing gas, excluding the inert gas.
  • the flow rate of the hydrogen fluoride gas in step S13 is 70% by volume or more, 80% by volume or more, 85% by volume or more, or 90% by volume with respect to the total flow rate of the first processing gas excluding the inert gas. % or more or 95 volume % or more.
  • the flow rate of the hydrogen fluoride gas is set to the total flow rate of the first processing gas excluding the inert gas.
  • the flow rate of the hydrogen fluoride gas is adjusted to 70% by volume or more and 96% by volume or less with respect to the total flow rate of the first processing gas excluding the inert gas.
  • the flow rate of the hydrogen fluoride gas in the first processing gas excluding the inert gas within such a range, it is possible to etch the film SF1 at a high etching rate while suppressing the etching of the mask MSK. can.
  • the etching selectivity of the silicon-containing film to the etching of the mask can be 5 or more.
  • the film SF1 can be etched at an effective rate.
  • the amount of deposition gas such as carbon-containing gas can be suppressed, so that not only the risk of clogging the mask MSK can be reduced, but also the cleaning time in the plasma processing chamber 10 can be shortened. can be reduced to 50% or less.
  • the selectivity may not be sufficiently improved.
  • the total flow rate of the first processing gas excluding the inert gas may be appropriately adjusted according to the chamber volume, and in one example, may be 100 sccm or more.
  • the first processing gas may contain carbon-containing gas in addition to hydrogen fluoride gas. Moreover, in addition to the hydrogen fluoride gas and the carbon-containing gas, at least one selected from the group consisting of an oxygen-containing gas and a halogen-containing gas may be included.
  • Carbon-containing gas includes, for example, at least one selected from the group consisting of fluorocarbon gas, hydrofluorocarbon gas, and hydrocarbon gas.
  • fluorocarbon gas for example CF4, C2F2, C2F4, C3F8, C4F6, C4F8 or C5F8 can be used.
  • hydrofluorocarbon gases examples include CHF3, CH2F2, CH3F, C2HF5, C2H2F4, C2H3F3, C2H4F2, C3HF7, C3H2F2, C3H2F6, C3H2F4, C3H3F5, C4H5F5, C4H2F6, C5H2F10, c-C5H3F7 or C3H2F4.
  • a hydrocarbon gas for example CH4, C2H6, C3H6, C3H8 or C4H10 can be used.
  • the carbon-containing gas may contain CO and/or CO2 in addition to the above.
  • a fluorocarbon gas and/or a hydrofluorocarbon gas having two or more carbon atoms can be used as the carbon-containing gas.
  • a fluorocarbon gas and/or a hydrofluorocarbon gas having 2 or more carbon atoms shape abnormalities such as bowing can be effectively suppressed.
  • a fluorocarbon gas and/or a hydrofluorocarbon gas having 3 or more carbon atoms shape abnormality can be further suppressed.
  • the fluorocarbon gas having 3 or more carbon atoms for example, C4F8 can be used.
  • the hydrofluorocarbon gas having 3 or more carbon atoms may contain an unsaturated bond and may contain one or more CF3 groups.
  • the hydrofluorocarbon gas having 3 or more carbon atoms for example, C3H2F4 or C4H2F6 can be used.
  • the first processing gas contains an oxygen-containing gas
  • an oxygen-containing gas for example, at least one selected from the group consisting of O2, CO, CO2, H2O and H2O2 can be used.
  • the etching shape can be controlled.
  • the halogen-containing gas include carbon-free fluorine-containing gases such as SF6, NF3, XeF2, SiF4, IF7, ClF5, BrF5, AsF5, NF5, PF3, PF5, POF3, BF3, HPF6, and WF6; , chlorine-containing gases such as SiCl4, CCl4, BCl3, PCl3, PCl5 and POCl3; bromine-containing gases such as HBr, CBr2F2, C2F5Br, PBr3, PBr5 and POBr3; At least one selected from the group consisting of iodine-containing gases such as can be used.
  • the first processing gas is a gas having a side wall protection effect, for example, a sulfur-containing gas such as COS; Contained gas may be included.
  • the phosphorus-containing gas having the effect of protecting the side wall includes the above-described phosphorous fluoride gas such as PF3 and PF5, and halogenated phosphorous gas including phosphorous chloride gas such as PCl3 and PCl5.
  • the first processing gas contains hydrogen fluoride and at least one carbon-containing gas selected from the group consisting of fluorocarbon gases and hydrofluorocarbon gases.
  • the carbon-containing gas may be a fluorocarbon gas as described above or a hydrofluorocarbon gas as described above.
  • the fluorocarbon gas may be C4F8.
  • the hydrofluorocarbon gas may be at least one selected from the group consisting of C3H2F4 and C4H2F6.
  • the first processing gas may further contain at least one selected from the group consisting of oxygen-containing gas and halogen-containing gas.
  • the halogen-containing gas may be at least one selected from the group consisting of halogen-containing gases containing halogen elements other than fluorine and fluorine-containing gases containing no carbon.
  • the additive gas may further include at least one selected from the group consisting of a sulfur-containing gas, a phosphorus-containing gas, and a boron-containing gas, which have a side wall protecting effect.
  • the first processing gas may contain an inert gas.
  • the inert gas in addition to nitrogen gas, rare gases such as Ar, Kr and Xe can be used.
  • the first processing gas is controlled so that the flow rate of the hydrogen fluoride gas with respect to the total flow rate of the first processing gas excluding these inert gases is the ratio described above.
  • the control unit 2 controls the gas supply unit 20 so as to supply the processing gas described above into the plasma processing chamber 10.
  • the control unit 2 controls the gas supply unit so that the flow rate of the hydrogen fluoride gas in the processing gas supplied into the plasma processing chamber 10 is 70% by volume or more of the total flow rate of the processing gas. 20.
  • the controller 2 controls the exhaust system 40 so that the pressure inside the plasma processing chamber 10 becomes the designated pressure.
  • the controller 2 controls each part of the power supply 30 to supply the first high frequency power and/or the second high frequency power to generate plasma from the process gas in the plasma processing chamber 10. , for example, the first RF generator 31a and/or the second RF generator 31b.
  • the second RF generator 31b applies a second high-frequency power (that is, high-frequency power for bias) of 5 W/cm 2 or more to the substrate support 11 in order to attract ions from the plasma to the substrate W. may be supplied.
  • the second high-frequency power of 5 W/cm 2 or higher allows ions from the plasma to sufficiently reach the bottom of the space (for example, space SP shown in FIG. 8) of film SF1 formed by etching.
  • a pulse voltage other than high frequency may be supplied to the substrate supporting portion 11 instead of the high frequency power for bias.
  • the pulse voltage is a pulse voltage supplied from a pulse power supply.
  • a pulsed power supply may be configured such that the power supply itself provides a pulsed wave, or may comprise a device downstream of the pulsed power supply for pulsing the voltage.
  • a pulse voltage is supplied to the substrate support 11 such that a negative potential is produced on the substrate W1.
  • the pulse voltage may be a negative DC voltage pulse.
  • the pulse voltage may be a square-wave pulse, a triangular-wave pulse, an impulse, or may have other voltage waveform pulses.
  • FIG. 9 is an example of a timing chart regarding the substrate processing method in the second embodiment.
  • the horizontal axis indicates time.
  • the vertical axis indicates the supply state of the first processing gas, the level of the first high-frequency power HF, and the level of the pulse voltage.
  • a first process gas is periodically supplied into plasma processing chamber 10 .
  • the pulse of the first high-frequency power and the pulse voltage are periodically supplied to the substrate supporting portion 11 .
  • the period during which the pulse of the first high-frequency power HF is supplied, the period during which the pulse voltage is supplied, and the period during which the first processing gas is supplied are synchronized.
  • the first processing gas may be continuously supplied into the plasma processing chamber 10 .
  • the "L" level of the first high frequency power HF means that the first high frequency power HF is not supplied or the power level of the first high frequency power HF is the power level indicated by "H". indicates that it is lower than
  • the "L" level of the pulse voltage indicates that the pulse voltage is not applied to the substrate supporting portion 11 or the level of the pulse voltage is lower than the level indicated by "H”.
  • "ON" for the supply state of the first processing gas indicates that the first processing gas is being supplied into the plasma processing chamber 10
  • "OFF" for the supply state of the first processing gas. indicates that the supply of the first process gas into the plasma processing chamber 10 is stopped.
  • the period during which the voltage level of the pulse voltage is L is defined as “L period”
  • the period during which the voltage level of the pulse voltage is H is defined as "H period”.
  • the frequency (first frequency) of the pulse voltage in the H period may be controlled from 100 kHz to 3.2 MHz. In one example, the first frequency is controlled at 400 kHz. In this case, the duty ratio (first duty ratio) indicating the ratio of the period in which the pulse voltage level is H in one cycle may be 50% or less, or may be 30% or less.
  • the frequency of the pulse voltage supplied periodically that is, the frequency (second frequency) that defines the cycle of the H period may be 1 kHz to 200 kHz or 5 Hz to 100 kHz.
  • the duty ratio (second duty ratio) indicating the proportion of the H period within one cycle may be 50% to 90%.
  • the case where the period during which the pulse of the first high-frequency power HF is supplied, the period during which the pulse voltage is supplied, and the period during which the first processing gas is supplied are synchronized has been described. , they may not be synchronized.
  • the temperature of the electrostatic chuck 1111 in step S13 By adjusting the temperature of the electrostatic chuck 1111 in step S13 to a low temperature, eg, ⁇ 50° C. or less, the adsorption of the etchant on the substrate surface is promoted, so that the etching rate can be improved.
  • the temperature of the electrostatic chuck 1111 may be adjusted according to the ratio of the phosphorus-containing gas in the first process gas.
  • FIG. 8 is a partially enlarged cross-sectional view showing an example of the substrate after performing the substrate processing method shown in FIG.
  • a space SP reaching, for example, the underlying layer UL is formed in the film SF1.
  • the temperature control system 50 can control the electrostatic chuck 1111 and the substrate W1 to a predetermined temperature in the process in the low temperature region.
  • FIG. 10 is a flowchart showing an example of substrate processing in the third embodiment.
  • the substrate processing method shown in FIG. 10 is applied to a substrate having a silicon-containing film.
  • the silicon-containing film is etched.
  • FIG. 11 is a partially enlarged cross-sectional view showing an example of the substrate provided in the third embodiment.
  • the substrate W2 shown in FIG. 11 can be used for manufacturing devices such as DRAM (Dynamic Random Access Memory) and 3D-NAND.
  • the substrate W2 has a silicon-containing film SF2.
  • the substrate W2 may further have a base region UR.
  • the silicon-containing film SF2 can be provided over the underlying region UR.
  • the silicon-containing film SF2 can be a silicon-containing dielectric film.
  • Silicon-containing dielectric films may include silicon oxide films or silicon nitride films.
  • the silicon-containing dielectric film may be a film having other film types as long as it is a film containing silicon.
  • the silicon-containing film SF2 may include a silicon film (for example, a polycrystalline silicon film).
  • the silicon-containing film SF2 may include at least one of a silicon nitride film, a polycrystalline silicon film, a carbon-containing silicon film, and a low dielectric constant film.
  • Carbon-containing silicon films may include SiC films and/or SiOC films.
  • the low dielectric constant film contains silicon and can be used as an interlayer insulating film.
  • the silicon-containing film SF2 may include two or more silicon-containing films having different film types.
  • the two or more silicon-containing films may include silicon oxide films and silicon nitride films.
  • the silicon-containing film SF2 may be, for example, a multilayer film including one or more silicon oxide films and one or more silicon nitride films alternately laminated.
  • the silicon-containing film SF2 may be a multilayer film including a plurality of alternately laminated silicon oxide films and a plurality of silicon nitride films.
  • the two or more silicon-containing films may include a silicon oxide film and a silicon film.
  • the silicon-containing film SF2 may be, for example, a multilayer film including one or more silicon oxide films and one or more silicon films alternately laminated.
  • the silicon-containing film SF2 may be a multilayer film including a plurality of alternately laminated silicon oxide films and a plurality of polycrystalline silicon films.
  • the two or more silicon-containing films may include a silicon oxide film, a silicon nitride film, and a silicon film.
  • the substrate W2 may further have a mask MK.
  • a mask MK is provided on the silicon-containing film SF2.
  • the mask MK is made of a material having an etching rate lower than that of the silicon-containing film SF2 in step S23 of the substrate processing method to be described later.
  • Mask MK may be formed from an organic material. That is, the mask MK may contain carbon.
  • the mask MK can be made of, for example, an amorphous carbon film, a photoresist film, or a spin-on carbon film (SOC film).
  • mask MK may be formed from a silicon-containing film, such as a silicon-containing anti-reflective coating.
  • mask MK may be a metal-containing mask formed from a metal-containing material such as titanium nitride, tungsten, tungsten carbide.
  • Mask MK may have a thickness of 3 ⁇ m or more.
  • the mask MK is patterned. That is, the mask MK has a pattern to be transferred to the silicon-containing film SF2 in step S23 of the substrate processing method.
  • openings such as holes or trenches are formed in the silicon-containing film SF2.
  • the aspect ratio of the opening formed in the silicon-containing film SF2 in step S23 may be 20 or more, or may be 30 or more, 40 or more, or 50 or more.
  • the mask MK may have a line-and-space pattern.
  • the substrate processing method of the third embodiment will be described by taking as an example the case where it is applied to the substrate W2 shown in FIG. 11 using the plasma processing system.
  • the substrate processing method can be executed in the plasma processing apparatus 1 by controlling each section of the plasma processing apparatus 1 by the control unit 2 .
  • the control of each part of the plasma processing apparatus 1 by the controller 2 for executing the substrate processing method will also be described.
  • FIG. 12(a) is a partially enlarged cross-sectional view of an example substrate to which the substrate processing method shown in FIG. 10 is applied
  • FIG. FIG. 4 is an enlarged partial cross-sectional view of an example substrate that has been etched.
  • FIG. 13 is an example of a timing chart regarding the substrate processing method according to the third embodiment.
  • the horizontal axis indicates time.
  • the vertical axis indicates the power level of the high-frequency power HF, the electrical bias level, and the supply state of the processing gas.
  • the “L” level of the high frequency power HF indicates that the high frequency power HF is not supplied or the power level of the high frequency power HF is lower than the power level indicated by "H".
  • the “L” level of the electrical bias indicates that no electrical bias is applied to the lower electrode or the level of the electrical bias is lower than the level indicated by "H”.
  • the processing gas supply state “ON” indicates that the processing gas is being supplied into the plasma processing chamber 10
  • the processing gas supply state “OFF” indicates that the processing gas is being supplied into the plasma processing chamber 10 . It indicates that the supply of processing gas is stopped.
  • the controller 2 controls the plasma processing apparatus 1 so that the substrate W2 is provided in the plasma processing chamber 10 (step S21).
  • a substrate W2 is placed on and held by the electrostatic chuck 1111 .
  • the control unit 2 controls the temperature control system 50 and starts temperature control processing so that the temperature of the substrate supporting unit 11 (electrostatic chuck 1111, substrate W1) reaches a predetermined temperature (step S22). That is, the control unit 2 instructs the control unit 60 of the temperature control system 50 to execute the temperature control process of the first embodiment. Note that the temperature control process is the same as that of the first embodiment, so the description thereof will be omitted.
  • the control unit 2 controls the plasma processing apparatus 1 to execute step SP when the temperature of the substrate W2 reaches a predetermined temperature due to the temperature control process.
  • step SP plasma processing is performed on the substrate W2.
  • step SP plasma is generated from the processing gas within the plasma processing chamber 10 .
  • the substrate processing method of the third embodiment includes step S23. Step S23 is performed during execution of step SP.
  • the substrate processing method of the third embodiment may further include step S24. Step S24 is performed during execution of step SP. Steps S23 and S24 may occur simultaneously or may be performed independently of each other.
  • step S23 the silicon-containing film SF2 is etched by chemical species from the plasma generated from the processing gas within the plasma processing chamber 10 in step SP.
  • a protective film PF is formed on the substrate W2 by chemical species from the plasma generated from the process gas in the plasma processing chamber 10 at step SP.
  • the protective film PF is formed on the sidewall surface defining the opening formed in the silicon-containing film SF2.
  • the processing gas used in step SP contains a halogen element and phosphorus.
  • a halogen element contained in the process gas may be fluorine.
  • the process gas may contain at least one halogen-containing molecule.
  • the process gas may contain at least one fluorocarbon or hydrofluorocarbon as the at least one halogen-containing molecule.
  • Fluorocarbons are, for example, at least one of CF4, C3F8, C4F6, or C4F8.
  • Hydrofluorocarbons are, for example, at least one of CH2F2, CHF3, or CH3F. Hydrofluorocarbons may contain more than one carbon. Hydrofluorocarbons may contain, for example, three carbons, or four carbons.
  • the process gas may contain at least one phosphorus-containing molecule.
  • the phosphorus-containing molecule may be an oxide such as tetraphosphorus decaoxide (P4O10), tetraphosphorus octaoxide (P4O8), tetraphosphorus hexaoxide (P4O6). Tetraphosphorus decaoxide is sometimes referred to as diphosphorus pentoxide (P2O5).
  • Phosphorus containing molecules are phosphorus trifluoride (PF3), phosphorus pentafluoride (PF5), phosphorus trichloride (PCl3), phosphorus pentachloride (PCl5), phosphorus tribromide (PBr3), phosphorus pentabromide (PBr5) , a halide such as phosphorus iodide (PI3). That is, the molecule containing phosphorus may contain fluorine as a halogen element. Alternatively, the phosphorus-containing molecule may contain a halogen element other than fluorine as the halogen element.
  • the phosphorus-containing molecule may be a phosphoryl halide such as phosphoryl fluoride (POF3), phosphoryl chloride (POCl3), phosphoryl bromide (POBr3).
  • Phosphorus-containing molecules may be phosphine (PH3), calcium phosphide (such as Ca3P2), phosphoric acid (H3PO4), sodium phosphate (Na3PO4), hexafluorophosphoric acid (HPF6), and the like.
  • Phosphorus-containing molecules may be fluorophosphines (HxPFy). where the sum of x and y is 3 or 5. Examples of fluorophosphines include HPF2 and H2PF3.
  • the process gas may contain, as the at least one phosphorus-containing molecule, one or more of the phosphorus-containing molecules described above.
  • the process gas can include at least one of PF3, PCl3, PF5, PCl5, POCl3, PH3, PBr3, or PBr5 as the at least one phosphorus-containing molecule.
  • each phosphorous-containing molecule contained in the processing gas can be vaporized by heating or the like and supplied into the plasma processing chamber 10 if it is liquid or solid.
  • the processing gas used in step SP may further contain carbon and hydrogen.
  • the process gas may include at least one of H2, hydrogen fluoride (HF), hydrocarbons (CxHy), hydrofluorocarbons (CHxFy), or NH3 as hydrogen-containing molecules. Hydrocarbons are for example CH4 or C3H6. where each of x and y is a natural number.
  • the process gas may include fluorocarbons or hydrocarbons (eg, CH4) as carbon-containing molecules.
  • the process gas may further contain oxygen.
  • the process gas may contain O2, for example. Alternatively, the process gas may be free of oxygen.
  • the process gas includes phosphorus-containing gas, fluorine-containing gas, and hydrogen-containing gas.
  • the hydrogen-containing gas contains at least one selected from the group consisting of hydrogen fluoride (HF), H2, ammonia (NH3), and hydrocarbons.
  • the phosphorus-containing gas contains at least one of the phosphorus-containing molecules described above.
  • the fluorine-containing gas includes at least one gas selected from the group consisting of fluorocarbon gases and carbon-free fluorine-containing gases.
  • a fluorocarbon gas is a gas containing the fluorocarbon described above.
  • the fluorine-containing gas that does not contain carbon is, for example, nitrogen trifluoride gas (NF3 gas) or sulfur hexafluoride gas (SF6 gas).
  • the processing gas may further contain a hydrofluorocarbon gas.
  • a hydrofluoro-carbon gas is a hydrofluorocarbon gas as described above.
  • the processing gas may further contain a halogen-containing gas containing a halogen element other than fluorine.
  • a halogen-containing gas is, for example, Cl2 gas and/or HBr gas.
  • An example process gas includes or consists essentially of a phosphorus-containing gas, a fluorocarbon gas, a hydrogen-containing gas, and an oxygen-containing gas (eg, O2 gas).
  • Another example process gas includes or substantially includes phosphorus-containing gases, carbon-free fluorine-containing gases, fluorocarbon gases, hydrogen-containing gases, hydrofluorocarbon gases, and halogen-containing gases containing halogen elements other than fluorine. It consists of these.
  • the process gas comprises or consists essentially of the phosphorous-containing gas described above, the fluorine-containing gas described above, the hydrofluorocarbon gas described above, and the halogen-containing gas containing a halogen element other than fluorine, described above. consists of
  • the processing gas may include a first gas and a second gas.
  • the first gas is a phosphorus-free gas. That is, the first gas is all gases other than the phosphorus-containing gas contained in the processing gas.
  • the first gas may contain a halogen element.
  • the first gas may comprise at least one halogen-containing molecule gas as described above.
  • the first gas may further contain carbon and hydrogen.
  • the first gas may further include the gas of molecules containing hydrogen and/or the gas of molecules containing carbon as described above.
  • the first gas may further contain oxygen.
  • the first gas may contain O2 gas. Alternatively, the first gas may not contain oxygen.
  • the second gas is a phosphorus-containing gas. That is, the second gas is the phosphorus-containing gas described above.
  • the second gas may comprise at least one phosphorus-containing molecule gas as described above.
  • the flow rate ratio which is the ratio of the flow rate of the second gas to the flow rate of the first gas, may be set to be greater than 0 and equal to or less than 0.5.
  • the flow rate ratio may be set to 0.075 or more and 0.3 or less.
  • the flow ratio may be set to 0.1 or more and 0.25 or less.
  • the processing gas is supplied into the plasma processing chamber 10 in step SP.
  • the pressure of the gas inside the plasma processing chamber 10 is set to a designated pressure.
  • the gas pressure in the plasma processing chamber 10 can be set to a pressure of 5 mTorr (0.65 Pa) or more and 100 mTorr (13.3 Pa) or less.
  • high-frequency power HF is supplied to generate plasma from the processing gas within the plasma processing chamber 10 .
  • a continuous wave of high frequency power HF may be supplied.
  • high frequency power LF may be used instead of high frequency power HF.
  • both high frequency power HF and electrical bias may be supplied.
  • a continuous wave of electrical bias may be applied to the lower electrode.
  • the power level of the high frequency power HF can be set to a level of 2 kW or more and 10 kW or less.
  • the power level of the high frequency power LF can be set to a level of 2 kW or higher.
  • the power level of the high frequency power LF may be set to a level of 10 kW or higher.
  • the control unit 2 controls the gas supply unit 20 to supply the processing gas into the plasma processing chamber 10 .
  • the controller 2 also controls the exhaust system 40 to set the pressure of the gas inside the plasma processing chamber 10 to a specified pressure.
  • the control unit 2 controls each unit of the power supply 30, such as the first RF generation unit 31a and the second RF generation unit 31b, so as to supply the high frequency power HF, the high frequency power LF, or the high frequency power HF and the electric bias. do.
  • the control unit 2 controls the gas supply unit 20 to supply the processing gas into the plasma processing chamber 10.
  • the controller 2 also controls the exhaust system 40 to set the pressure of the gas inside the plasma processing chamber 10 to a specified pressure.
  • the control unit 2 controls each unit of the power supply 30, such as the first RF generation unit 31a and the second RF generation unit 31b, so as to supply the high frequency power HF, the high frequency power LF, or the high frequency power HF and the electric bias. do.
  • the temperature of the substrate W2 at the start of step S23 may be set to ⁇ 50° C. or less.
  • the controller 2 can control the temperature control system 50 as described above.
  • step S23 the silicon-containing film SF2 is etched by halogen chemical species from plasma generated from the processing gas.
  • the portion exposed from the mask MK in the entire region of the silicon-containing film SF2 is etched (see FIG. 12(a)).
  • phosphorus-containing molecules molecules containing phosphorus and halogen elements such as PF3, halogen chemical species derived from such molecules contribute to the etching of the silicon-containing film SF2. Therefore, phosphorus-containing molecules containing phosphorus and halogen elements, such as PF3, increase the etching rate of the silicon-containing film SF2 in step S23.
  • step S24 the protective film PF is formed on the side wall surfaces defining the opening formed in the silicon-containing film SF2 by the etching in step S23 (see FIG. 12(a)).
  • the protective film PF is formed by chemical species from the plasma generated from the process gas within the plasma processing chamber 10 in step SP.
  • Step S24 may proceed simultaneously with step S23.
  • the protective film PF may be formed such that its thickness decreases along the depth direction of the opening formed in the silicon-containing film SF2. .
  • the protective film PF contains silicon and phosphorus contained in the processing gas used in step SP. In one embodiment, the protective film PF may further contain carbon and/or hydrogen contained in the process gas. In one embodiment, the protective film PF may further contain oxygen contained in the processing gas or contained in the silicon-containing film SF2. In one embodiment, the protective film PF may contain a bond between phosphorus and oxygen.
  • the process gas plasma described above includes a plasma generated from hydrogen fluoride.
  • hydrogen fluoride may be the most abundant chemical species contained in the plasma generated from the process gas.
  • the presence of phosphorus species generated from the phosphorus-containing gas (the gas containing the phosphorus-containing molecules described above) on the surface of the substrate W2 promotes the adsorption of hydrogen fluoride, ie, an etchant, to the substrate W2. That is, in a state where the phosphorus chemical species generated from the phosphorus-containing gas exists on the surface of the substrate W2, the supply of the etchant to the bottom of the opening (recess) is promoted, and the etching rate of the silicon-containing film SF2 is increased.
  • the silicon-containing film SF2 is also etched in the lateral direction, as shown in FIG. 12(b). As a result, the width of the opening formed in the silicon-containing film SF2 is partially widened. For example, the width of the opening formed in the silicon-containing film SF2 is partially widened in the vicinity of the mask MK.
  • the protective film PF is formed on the sidewall surface defining the opening formed in the silicon-containing film SF2 by etching.
  • the silicon-containing film SF2 is etched while the sidewall surface is protected by the protective film PF. Therefore, according to the substrate processing method of the third embodiment, etching in the lateral direction can be suppressed in the plasma etching of the silicon-containing film SF2.
  • one or more cycles are sequentially performed during the period during which step SP is continued, i.e., during the period during which plasma is generated from the process gas in step SP.
  • step SP two or more cycles may be executed in sequence.
  • the electrical bias pulse wave described above may be applied to the lower electrode from the second RF generator 31b in step SP. That is, when plasma generated from the process gas exists in the plasma processing chamber 10, a pulse wave of electrical bias may be applied from the second RF generator 31b to the lower electrode.
  • the etching of the silicon-containing film SF2 in step S23 mainly occurs during the H period within the period of the electrical bias pulse wave.
  • the formation of the protective film PF in step S24 mainly occurs during the L period within the cycle of the pulse wave of the electrical bias.
  • the power level of the high frequency power LF can be set to a level of 2 kW or more in the H period within the cycle of the pulse wave of the electrical bias.
  • the power level of the high frequency power LF may be set to a level of 10 kW or more in the H period within the period of the pulse wave of the electrical bias.
  • the pulse wave of the high frequency power HF described above may be supplied in step SP.
  • the power level of the high frequency power HF can be set to a level of 1 kW or more and 10 kW or less.
  • the period of the pulse wave of the high frequency power HF may be synchronized with the period of the pulse wave of the electrical bias.
  • the H period in the cycle of the pulse wave of the high frequency power HF may be synchronized with the H period in the cycle of the pulse wave of the electrical bias.
  • the H period in the cycle of the pulse wave of the high frequency power HF may not be synchronized with the H period in the cycle of the pulse wave of the electrical bias.
  • the time length of the H period in the cycle of the pulse wave of the high frequency power HF may be the same as or different from the time length of the H period in the cycle of the pulse wave of the electrical bias.
  • the temperature control system 50 is a temperature control system that cools the members (the electrostatic chuck 1111 and the substrate W) in the plasma processing chamber 10, and at least one of C3F8 and C3H2F4 is A condenser 53 for condensing the temperature control medium, a heat exchanger 56 for cooling the temperature control medium condensed by the condenser 53, and heat exchange by the temperature control medium cooled by the heat exchanger 56 to cool the member to -150°C.
  • the temperature control unit (base 1110) for cooling to ⁇ 50° C. or less and the pump 55 for circulating the temperature control medium are provided. As a result, the temperature control system 50 can be used in low temperature regions.
  • the viscosity of the temperature control medium is 6 mPa ⁇ sec or less. As a result, the load on the pump 55 can be reduced even in the low temperature range.
  • the temperature control system 50 is a temperature control system that cools the members (the electrostatic chuck 1111 and the substrate W) inside the plasma processing chamber 10, and is a temperature control system that is in a gaseous state at normal temperature and normal pressure.
  • the temperature control system 50 can be used in low temperature regions.
  • the temperature control system 50 cools the members (the electrostatic chuck 1111 and the substrate W) in the plasma processing chamber 10 using a temperature control medium in a gaseous state at normal temperature and normal pressure.
  • the heat exchanger 56 that cools the condensed temperature control medium, the temperature control unit (base 1110) that cools the member by heat exchange with the temperature control medium cooled by the heat exchanger 56, and the temperature control medium and a pump 55 for circulating the As a result, the temperature control system 50 can be used in low temperature regions.
  • the temperature control medium that has undergone heat exchange in the temperature control unit is again condensed and liquefied by the condenser 53 that condenses the temperature control medium.
  • the temperature control medium that has turned into a gas phase after heat exchange can be returned to a liquid phase and circulated.
  • the temperature control medium is cooled to a predetermined temperature by the heat exchanger 56 .
  • the temperature control medium at a predetermined temperature can be circulated through the temperature control section.
  • the temperature control medium has a viscosity of 6 mPa ⁇ sec or less at a predetermined temperature. As a result, the load on the pump 55 can be reduced even in the low temperature range.
  • the temperature control medium is in a liquid phase at a predetermined temperature and in an equilibrium state above atmospheric pressure. As a result, it can be easily circulated by the pump 55 in the low temperature region. In addition, since the vapor pressure of the temperature control medium is sufficiently low, deterioration of cooling performance due to dryout can be suppressed.
  • the temperature control medium is allowed to contain a gas phase in the flow path inside the temperature control unit.
  • the member can be controlled to the target temperature even if the member receives heat input from the plasma due to high RF power.
  • the temperature control medium is C3F8 or C3H2F4.
  • the temperature control system 50 can be used in low temperature regions.
  • the predetermined temperature is a temperature in the range of -150°C or higher and -50°C or lower. As a result, it is possible to suppress an increase in the viscosity of the temperature control medium in the low temperature range. In addition, since the vapor pressure of the temperature control medium is sufficiently low, deterioration of cooling performance due to dryout can be suppressed.
  • the heat exchanger 56 cools the temperature control medium by heat exchange with the refrigerant. As a result, the temperature control medium can be cooled to a predetermined temperature.
  • the coolant is liquid nitrogen.
  • the temperature control medium can be cooled to a predetermined temperature.
  • the member is the substrate mounting table (substrate support portion 11). As a result, the substrate W can be cooled to a predetermined temperature.
  • the heat input to the member is 1 kW or more.
  • the member can be controlled to the target temperature even if the member receives heat input from the plasma due to high RF power.
  • the temperature control method is a temperature control method for cooling the members (the electrostatic chuck 1111 and the substrate W) in the plasma processing chamber 10, and a) is in a gaseous state at normal temperature and normal pressure.
  • It has a step of returning the temperature control medium to the condenser and a step of repeating f) a) to e).
  • the vapor pressure of the temperature control medium is sufficiently low, deterioration of cooling performance due to dryout can be suppressed.
  • the electrostatic chuck 1111 and the substrates W, W1, and W2 are described as examples of the members to be cooled, but the members are not limited to this.
  • the members to be cooled may be members requiring cooling, such as the showerhead 13, the upper electrode, the sidewall 10a of the plasma processing chamber 10, the ring assembly 112, and the like.
  • the plasma processing apparatus 1 that performs processing such as etching on the substrates W, W1, and W2 using capacitively-coupled plasma as a plasma source has been described as an example. is not limited to If the apparatus processes the substrates W, W1, and W2 using plasma, the plasma source is not limited to capacitively coupled plasma, and any plasma source such as inductively coupled plasma, microwave plasma, magnetron plasma, etc. can be used.
  • the step of controlling the temperature of the substrate support includes: a) a step of condensing a temperature control medium containing at least one selected from the group consisting of C3F8 and C3H2F4 in a condenser; b) cooling the temperature control medium condensed in the condenser with a heat exchanger; c) supplying the temperature control medium cooled to ⁇ 150° C. or more and ⁇ 50° C.
  • a substrate processing apparatus a plasma processing chamber comprising a substrate support within which a substrate rests; a temperature control system that controls the temperature of the substrate support; a control unit; the controller configured to control the substrate processing apparatus to provide the substrate having a silicon-containing film including a silicon oxide film and a mask on the silicon-containing film in the plasma processing chamber;
  • the control unit is configured to control the temperature control system to control the temperature of a substrate support on which the substrate is placed,
  • the control unit is a first processing gas containing hydrogen fluoride gas and at least one carbon-containing gas selected from the group consisting of fluorocarbon gas and hydrofluorocarbon gas, and the first processing gas excluding an inert gas.
  • the substrate processing apparatus is configured to be controlled to etch the silicon-containing film by plasma generated from the first processing gas having the highest flow rate of the hydrogen fluoride gas among the first processing gases,
  • the control unit controls the temperature control system
  • a) the control unit is configured to control the temperature control system to condense a temperature control medium containing at least one selected from the group consisting of C3F8 and C3H2F4 in a condenser;
  • the control unit is configured to b) control the temperature control system so that the temperature control medium condensed by the condenser is cooled by a heat exchanger,
  • the control unit c) supplies the temperature control medium cooled to ⁇ 150° C. or more and ⁇ 50° C.
  • the control unit is configured to control the temperature control system in the temperature control unit so as to cool the substrate support portion by heat exchange with the temperature control medium;
  • the control unit is configured to e) control the temperature control system to return the temperature control medium after heat exchange in the temperature control unit to the condenser,
  • the control unit is configured to control the temperature control system to repeat a) to e), Substrate processing equipment.
  • step 3 providing in a plasma processing chamber a substrate having a silicon-containing film comprising a silicon oxide film and a mask over the silicon-containing film; controlling the temperature of a substrate support on which the substrate is placed; etching the silicon-containing film with a plasma generated from a process gas containing phosphorus-containing gas and hydrogen fluoride; has
  • the step of controlling the temperature of the substrate support includes: a) a step of condensing a temperature control medium in a gaseous state at normal temperature and pressure with a condenser; b) cooling the temperature control medium condensed in the condenser with a heat exchanger; c) supplying the temperature control medium cooled to ⁇ 150° C. or more and ⁇ 50° C.
  • a substrate processing apparatus a plasma processing chamber comprising a substrate support within which a substrate rests; a temperature control system that controls the temperature of the substrate support; a control unit; the controller configured to control the substrate processing apparatus to provide a substrate having a silicon-containing film including a silicon oxide film and a mask on the silicon-containing film in a plasma processing chamber;
  • the controller is configured to control the temperature control system to control the temperature of a substrate support on which the substrate is placed,
  • the control unit is configured to control the substrate processing apparatus to etch the silicon-containing film with plasma generated from a process gas containing phosphorus-containing gas and hydrogen fluoride,
  • the control unit controls the temperature control system,
  • the control unit a) is configured to control the temperature control system so as to condense a temperature control medium that is in a gaseous state at normal temperature and normal pressure in a condenser,
  • the control unit is configured to b) control the temperature control system so that the temperature control medium condensed by the condenser is cooled by
  • control unit configured to control the d) the control unit is configured to control the temperature control system in the temperature control unit so as to cool the substrate support portion by heat exchange with the temperature control medium;
  • the control unit is configured to e) control the temperature control system to return the temperature control medium after heat exchange in the temperature control unit to the condenser,
  • the control unit is f) configured to control the temperature control system to repeat a) to e). Substrate processing equipment.
  • plasma processing apparatus 10 plasma processing chamber 11 substrate support 50 temperature control system 51a to 51f piping 52 gas supply 53 condenser 54 cooling jacket 55 pump 56 heat exchanger 111 main body 112 ring assembly 1110 base 1110a flow path 1111 static Electric chuck W, W1, W2 Substrate

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PCT/JP2022/007982 2022-02-25 2022-02-25 温調システム、温調方法、基板処理方法及び基板処理装置 Ceased WO2023162161A1 (ja)

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