WO2022230118A1 - エッチング方法 - Google Patents

エッチング方法 Download PDF

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Publication number
WO2022230118A1
WO2022230118A1 PCT/JP2021/017012 JP2021017012W WO2022230118A1 WO 2022230118 A1 WO2022230118 A1 WO 2022230118A1 JP 2021017012 W JP2021017012 W JP 2021017012W WO 2022230118 A1 WO2022230118 A1 WO 2022230118A1
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WO
WIPO (PCT)
Prior art keywords
gas
film
etching
silicon
etching method
Prior art date
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/JP2021/017012
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English (en)
French (fr)
Japanese (ja)
Inventor
幕樹 戸村
貴俊 大類
圭恵 熊谷
隆太郎 須田
聡 大内田
悠輔 若生
嘉英 木原
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=83848133&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2022230118(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Tokyo Electron Ltd filed Critical Tokyo Electron Ltd
Priority to JP2023514954A priority Critical patent/JP7336623B2/ja
Priority to KR1020237007617A priority patent/KR102737019B1/ko
Priority to KR1020247039533A priority patent/KR20250005413A/ko
Priority to CN202180054563.7A priority patent/CN116034454A/zh
Priority to PCT/JP2021/017012 priority patent/WO2022230118A1/ja
Priority to TW110116004A priority patent/TWI890783B/zh
Priority to TW114123571A priority patent/TW202538867A/zh
Publication of WO2022230118A1 publication Critical patent/WO2022230118A1/ja
Priority to JP2023041775A priority patent/JP7639042B2/ja
Priority to US18/140,694 priority patent/US20230268191A1/en
Anticipated expiration legal-status Critical
Priority to JP2025024843A priority patent/JP2025068048A/ja
Priority to US19/245,988 priority patent/US20250323055A1/en
Ceased legal-status Critical Current

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    • 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
    • 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
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32082—Radio frequency generated discharge
    • H01J37/32091—Radio frequency generated discharge the radio frequency energy being capacitively coupled to the plasma
    • 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
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32082—Radio frequency generated discharge
    • H01J37/32137—Radio frequency generated discharge controlling of the discharge by modulation of energy
    • H01J37/32155—Frequency modulation
    • H01J37/32165—Plural frequencies
    • 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
    • H10P50/26—Dry etching; Plasma etching; Reactive-ion etching of conductive or resistive materials
    • H10P50/264—Dry etching; Plasma etching; Reactive-ion etching of conductive or resistive materials by chemical means
    • H10P50/266—Dry etching; Plasma etching; Reactive-ion etching of conductive or resistive materials by chemical means by vapour etching only
    • H10P50/267—Dry etching; Plasma etching; Reactive-ion etching of conductive or resistive materials by chemical means by vapour etching only using plasmas
    • H10P50/268—Dry etching; Plasma etching; Reactive-ion etching of conductive or resistive materials by chemical means by vapour etching only using plasmas of silicon-containing layers
    • 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
    • H10P50/71—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
    • 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
    • H01J2237/3341—Reactive etching

Definitions

  • Exemplary embodiments of the present disclosure relate to etching methods, process gases, and plasma processing apparatuses.
  • Plasma etching uses a plasma generated from a process gas to etch a silicon-containing film.
  • US Patent Application Publication No. 2016/0343580 discloses process gases including fluorocarbon gases as process gases used for plasma etching of silicon-containing films.
  • Japanese Patent Laying-Open No. 2016-39310 discloses a processing gas containing a hydrocarbon gas and a hydrofluorocarbon gas as a processing gas used for plasma etching of a silicon-containing film.
  • the present disclosure provides techniques for increasing the selectivity of etching silicon-containing films to etching masks in plasma etching.
  • an etching method includes step (a) of providing a substrate in a chamber of a plasma processing apparatus.
  • a substrate includes a silicon-containing film and a mask.
  • a mask is provided on the silicon-containing film.
  • the etching method further includes step (b) of etching the silicon-containing film with species from a plasma generated from the process gas within the chamber.
  • the process gas includes hydrogen fluoride gas and carbon-containing gas. Hydrogen fluoride gas has the highest flow rate among all gas flow rates in the process gas that does not contain a noble gas. Alternatively, the flow rate of hydrogen fluoride gas is the largest among the flow rates of all the gases other than the rare gas in the processing gas.
  • FIG. 1 is a flow diagram of an etching method according to one exemplary embodiment
  • 2 is a partially enlarged cross-sectional view of an example substrate to which the etching method shown in FIG. 1 can be applied
  • FIG. 1 schematically illustrates a plasma processing apparatus according to one exemplary embodiment
  • FIG. 2 is a partially enlarged cross-sectional view of an exemplary substrate to which the etching method shown in FIG. 1 is applied
  • FIG. FIG. 4 is an example timing chart for an etching method according to one exemplary embodiment
  • FIGS. 6(a), 6(b), and 6(c) is an exemplary timing chart of the flow rate of the carbon-containing gas and the pressure within the chamber. (a) of FIG.
  • FIG. 7 is a partially enlarged cross-sectional view of an example substrate obtained when the flow rate of the carbon-containing gas is high, and (b) of FIG. FIG. 4 is a partially enlarged cross-sectional view of an example substrate obtained when not supplied;
  • FIG. 8(a) is a partially enlarged sectional view of an example substrate obtained when the pressure in the chamber is high, and
  • FIG. 8(b) is an example substrate obtained when the pressure in the chamber is low.
  • 1 is a partially enlarged cross-sectional view of FIG.
  • FIG. 4 is a graph showing the results of the first experiment; 10 is a graph showing the results of a second experiment; 11(a), 11(b), and 11(c) are cross-sectional photographs of the 12th sample substrate, the 15th sample substrate, and the 16th sample substrate after plasma etching, respectively. .
  • FIG. 12(a) is a graph showing the results of the fifth experiment, and FIG. 12(b) is a graph showing the results of the sixth experiment.
  • 10 is a graph showing results of a seventh experiment;
  • FIG. 11 is a graph showing the results of eighth to eleventh experiments;
  • FIG. FIG. 14 is a plan view of a sample substrate used in the 12th experiment and the 13th experiment;
  • FIG. 11 is a graph showing the results of 14th to 18th experiments;
  • an etching method includes step (a) of providing a substrate in a chamber of a plasma processing apparatus.
  • a substrate includes a silicon-containing film and a mask.
  • a mask is provided on the silicon-containing film.
  • the etching method further includes step (b) of etching the silicon-containing film with species from a plasma generated from the process gas within the chamber.
  • the process gas includes hydrogen fluoride gas and carbon-containing gas. Hydrogen fluoride gas has the highest flow rate among all gas flow rates in the process gas that does not contain a noble gas. Alternatively, the flow rate of hydrogen fluoride gas is the largest among the flow rates of all the gases other than the rare gas in the processing gas.
  • carbon species generated from the carbon-containing gas are deposited on the mask to protect it.
  • the etchant generated from hydrogen fluoride has a small mass, but is excellent in the ability to etch silicon-containing films. Therefore, according to the above embodiment, the selectivity of etching the silicon-containing film with respect to the etching of the mask is increased.
  • the process gas may further contain a phosphorus-containing gas. This results in a higher etch rate of the silicon-containing film, resulting in a higher selectivity of etching the silicon-containing film relative to etching the mask.
  • the processing gas may further contain an amine-based gas. This results in a higher etch rate of the silicon-containing film, resulting in a higher selectivity of etching the silicon-containing film relative to etching the mask.
  • the carbon-containing gas may include fluorocarbons and/or hydrofluorocarbons having 1 or more and 6 or less carbon atoms in the molecule.
  • step (b) the flow rate of the carbon-containing gas may be decreased stepwise.
  • the pressure in the chamber may be set to 0.666 Pascal or higher and 2.666 Pascal or lower.
  • a plasma processing method includes step (a) of preparing a substrate in a chamber of a plasma processing apparatus.
  • a substrate includes a silicon-containing film and a mask.
  • a mask is provided on the silicon-containing film.
  • the etching method further includes step (b) of etching the silicon-containing film with species from a plasma generated from the process gas within the chamber.
  • the processing gas contains hydrogen fluoride gas and further contains phosphorus-containing gas or amine-based gas.
  • Hydrogen fluoride gas has the highest flow rate among all gas flow rates in the process gas that does not contain a noble gas. Alternatively, the flow rate of hydrogen fluoride gas is the largest among the flow rates of all the gases other than the rare gas in the processing gas.
  • the process gas may further include one or more of each of NF3 , O2 , CO2 , CO, N2 , He, Ar, Kr, and Xe. good.
  • the process gas may further include a halogen-containing gas.
  • the halogen - containing gas is Cl2 , Br2 , HCl, HBr , HI, BCl3 , CHxCly , CFxBry , CFxIy , ClF3 , IF5 , IF7 , BrF3 . It may contain one or more gases of Here, x and y are integers of 1 or more.
  • the process gas may further include an iodine-containing gas.
  • the iodine-containing gas may include one or more of HI , IFt , and CxFyIz .
  • t, x, y, and z are integers of 1 or more.
  • step (b) the pressure within the chamber may be reduced stepwise.
  • the silicon-containing film may include a silicon oxide film and/or a silicon nitride film.
  • the silicon-containing film may further include a polycrystalline silicon film.
  • the mask may be a carbon-containing mask.
  • FIG. 1 is a flow diagram of an etching method according to one exemplary embodiment.
  • the etching method shown in FIG. 1 (hereinafter referred to as "method MT") is applied to a substrate having a silicon-containing film.
  • method MT the silicon-containing film is etched.
  • FIG. 2 is a partially enlarged cross-sectional view of an example substrate to which the etching method shown in FIG. 1 can be applied.
  • the substrate W shown in FIG. 2 can be used for manufacturing devices such as DRAM, 3D-NAND.
  • the substrate W has a membrane SF and a mask MK.
  • the substrate W may further have an underlying region UR.
  • the film SF can be provided on the base region UR.
  • a mask MK is provided on the membrane SF.
  • the film SF is a silicon-containing film. That is, the film SF contains silicon.
  • the film SF may be a single layer film or a multilayer film.
  • the film SF is a silicon film such as a silicon oxide film, a silicon nitride film, a polycrystalline silicon film, a carbon-containing silicon film such as a SiC film, or a low dielectric constant film.
  • the low dielectric constant film is, for example, a film used as an interlayer insulating film, and is formed of SiOC, SiOF, SiCOH, or the like.
  • Film SF includes at least one of a silicon oxide film and a silicon nitride film when it is a multilayer film.
  • Film SF may further include a polycrystalline silicon film when it is a multilayer film.
  • the film SF may include alternate lamination of a plurality of silicon oxide films and a plurality of silicon nitride films.
  • the film SF may include alternate lamination of a plurality of silicon oxide films and a plurality of silicon films (for example, polycrystalline silicon films).
  • Film SF may include a silicon oxide film, a silicon nitride film, and a polycrystalline silicon film.
  • the mask MK is made of a material having an etching rate lower than that of the film SF in the step STb.
  • Mask MK may be formed from an organic material. That is, the mask MK may be a carbon-containing mask.
  • the mask MK can be made of, for example, an amorphous carbon film, a photoresist film, a spin-on carbon film (SOC film), or a boron carbide 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, titanium oxide, 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 film SF in step STb.
  • the pattern of the mask MK is transferred to the film SF, recesses such as holes or trenches are formed in the film SF.
  • the aspect ratio of the recesses formed in the film SF in the step STb may be 20 or more, 30 or more, 40 or more, or 50 or more.
  • the mask MK may have a line-and-space pattern.
  • FIG. 3 is a schematic diagram of a plasma processing apparatus according to one exemplary embodiment.
  • a plasma processing apparatus 1 shown in FIG. 3 includes a chamber 10 .
  • Chamber 10 provides an interior space 10s therein.
  • Chamber 10 includes a chamber body 12 .
  • the chamber body 12 has a substantially cylindrical shape.
  • the chamber body 12 is made of aluminum, for example.
  • a corrosion-resistant film is provided on the inner wall surface of the chamber body 12 .
  • Corrosion resistant membranes can be formed from ceramics such as aluminum oxide, yttrium oxide.
  • a passage 12p is formed in the side wall of the chamber body 12.
  • the substrate W is transferred between the internal space 10s and the outside of the chamber 10 through the passageway 12p.
  • the passage 12p is opened and closed by a gate valve 12g.
  • a gate valve 12 g is provided along the side wall of the chamber body 12 .
  • a support 13 is provided on the bottom of the chamber body 12 .
  • the support portion 13 is made of an insulating material.
  • the support portion 13 has a substantially cylindrical shape.
  • the support portion 13 extends upward from the bottom portion of the chamber main body 12 in the internal space 10s.
  • the support portion 13 supports the substrate supporter 14 .
  • the substrate supporter 14 is configured to support the substrate W within the internal space 10s.
  • the substrate support 14 has a lower electrode 18 and an electrostatic chuck 20 .
  • Substrate support 14 may further include an electrode plate 16 .
  • the electrode plate 16 is made of a conductor such as aluminum and has a substantially disk shape.
  • a lower electrode 18 is provided on the electrode plate 16 .
  • the lower electrode 18 is made of a conductor such as aluminum and has a substantially disk shape. Lower electrode 18 is electrically connected to electrode plate 16 .
  • the electrostatic chuck 20 is provided on the lower electrode 18 .
  • a substrate W is placed on the upper surface of the electrostatic chuck 20 .
  • the electrostatic chuck 20 has a body and electrodes.
  • the main body of the electrostatic chuck 20 has a substantially disk shape and is made of a dielectric.
  • the electrode of the electrostatic chuck 20 is a film-like electrode and is provided inside the main body of the electrostatic chuck 20 .
  • Electrodes of the electrostatic chuck 20 are connected to a DC power supply 20p via a switch 20s. When a voltage is applied to the electrodes of the electrostatic chuck 20 from the DC power supply 20p, an electrostatic attractive force is generated between the electrostatic chuck 20 and the substrate W. As shown in FIG. The substrate W is attracted to the electrostatic chuck 20 by its electrostatic attraction and held by the electrostatic chuck 20 .
  • An edge ring 25 is arranged on the substrate supporter 14 .
  • the edge ring 25 is a ring-shaped member.
  • Edge ring 25 may be formed from silicon, silicon carbide, quartz, or the like.
  • a substrate W is placed on the electrostatic chuck 20 and within the area surrounded by the edge ring 25 .
  • a channel 18 f is provided inside the lower electrode 18 .
  • a heat exchange medium (for example, a refrigerant) is supplied to the flow path 18f from a chiller unit provided outside the chamber 10 through a pipe 22a.
  • the heat exchange medium supplied to the flow path 18f is returned to the chiller unit via the pipe 22b.
  • the temperature of the substrate W placed on the electrostatic chuck 20 is adjusted by heat exchange between the heat exchange medium and the lower electrode 18 .
  • a gas supply line 24 is provided in the plasma processing apparatus 1 .
  • the gas supply line 24 supplies the gap between the upper surface of the electrostatic chuck 20 and the back surface of the substrate W with a heat transfer gas (for example, He gas) from a heat transfer gas supply mechanism.
  • a heat transfer gas for example, He gas
  • the plasma processing apparatus 1 further includes an upper electrode 30 .
  • the upper electrode 30 is provided above the substrate support 14 .
  • the upper electrode 30 is supported above the chamber body 12 via a member 32 .
  • the member 32 is made of an insulating material.
  • Upper electrode 30 and member 32 close the upper opening of chamber body 12 .
  • the upper electrode 30 may include a top plate 34 and a support 36.
  • the bottom surface of the top plate 34 is the bottom surface on the side of the internal space 10s, and defines the internal space 10s.
  • the top plate 34 can be made of a low-resistance conductor or semiconductor that generates little Joule heat.
  • the top plate 34 has a plurality of gas discharge holes 34a passing through the top plate 34 in the plate thickness direction.
  • the support 36 detachably supports the top plate 34 .
  • Support 36 is formed from a conductive material such as aluminum.
  • a gas diffusion chamber 36 a is provided inside the support 36 .
  • the support 36 has a plurality of gas holes 36b extending downward from the gas diffusion chamber 36a.
  • the multiple gas holes 36b communicate with the multiple gas discharge holes 34a, respectively.
  • the support 36 is formed with a gas introduction port 36c.
  • the gas introduction port 36c is connected to the gas diffusion chamber 36a.
  • a gas supply pipe 38 is connected to the gas inlet 36c.
  • a gas source group 40 is connected to the gas supply pipe 38 via a flow controller group 41 and a valve group 42 .
  • the flow controller group 41 and the valve group 42 constitute a gas supply section.
  • the gas supply section may further include a gas source group 40 .
  • Gas source group 40 includes a plurality of gas sources.
  • the plurality of gas sources includes sources of process gases used in method MT.
  • the flow controller group 41 includes a plurality of flow controllers. Each of the plurality of flow controllers in the flow controller group 41 is a mass flow controller or a pressure-controlled flow controller.
  • the valve group 42 includes a plurality of open/close valves.
  • Each of the plurality of gas sources of the gas source group 40 is connected to the gas supply pipe 38 via a corresponding flow controller of the flow controller group 41 and a corresponding opening/closing valve of the valve group 42 .
  • a shield 46 is detachably provided along the inner wall surface of the chamber main body 12 and the outer circumference of the support portion 13. Shield 46 prevents reaction by-products from adhering to chamber body 12 .
  • the shield 46 is constructed, for example, by forming a corrosion-resistant film on the surface of a base material made of aluminum. Corrosion resistant membranes may be formed from ceramics such as yttrium oxide.
  • a baffle plate 48 is provided between the support portion 13 and the side wall of the chamber body 12 .
  • the baffle plate 48 is constructed, for example, by forming a corrosion-resistant film (film of yttrium oxide or the like) on the surface of a member made of aluminum.
  • a plurality of through holes are formed in the baffle plate 48 .
  • An exhaust device 50 is connected through an exhaust pipe 52 to the exhaust port 12e.
  • the evacuation device 50 includes a pressure regulating valve and a vacuum pump such as a turbomolecular pump.
  • the plasma processing apparatus 1 includes a high frequency power supply 62 and a bias power supply 64.
  • a high-frequency power supply 62 is a power supply that generates high-frequency power HF.
  • the high frequency power HF has a first frequency suitable for plasma generation.
  • the first frequency is, for example, a frequency within the range of 27 MHz to 100 MHz.
  • a high frequency power supply 62 is connected to the lower electrode 18 via a matching box 66 and the electrode plate 16 .
  • the matching device 66 has a circuit for matching the impedance on the load side (lower electrode 18 side) of the high frequency power supply 62 with the output impedance of the high frequency power supply 62 .
  • the high-frequency power supply 62 may be connected to the upper electrode 30 via a matching device 66 .
  • the high-frequency power supply 62 constitutes an example of a plasma generator.
  • a bias power supply 64 is a power supply that generates an electrical bias.
  • a bias power supply 64 is electrically connected to the lower electrode 18 .
  • the electrical bias has a second frequency.
  • the second frequency is lower than the first frequency.
  • the second frequency is, for example, a frequency within the range of 400 kHz-13.56 MHz.
  • An electrical bias is applied to the substrate support 14 (in one example, the bottom electrode 18) to attract ions to the substrate W when used with high frequency power HF.
  • the potential of the substrate W placed on the substrate support 14 fluctuates within a period defined by the second frequency.
  • the electrical bias may be applied to an electrode of the substrate support 14 other than the lower electrode 18, such as an electrode provided inside the electrostatic chuck 20.
  • the electrical bias may be high frequency power LF having a second frequency.
  • the radio frequency power LF is used as radio frequency bias power for drawing ions into the substrate W when used together with the radio frequency power HF.
  • a bias power supply 64 configured to generate high frequency power LF is connected to the lower electrode 18 via a matcher 68 and the electrode plate 16 .
  • the matching device 68 has a circuit for matching the impedance on the load side (lower electrode 18 side) of the bias power supply 64 with the output impedance of the bias power supply 64 .
  • Plasma may be generated by using the high-frequency power LF instead of the high-frequency power HF, that is, by using only a single high-frequency power.
  • the frequency of the high frequency power LF may be greater than 13.56 MHz, for example 40 MHz.
  • the plasma processing apparatus 1 does not need to include the high frequency power supply 62 and the matching box 66 .
  • the bias power supply 64 constitutes an example plasma generator.
  • the electrical bias may be a voltage pulse wave.
  • a voltage pulse wave is periodically generated and applied to the lower electrode 18 .
  • a period of the voltage pulse wave is defined at the second frequency. That is, the time length of the cycle of the voltage pulse wave is the reciprocal of the second frequency.
  • the voltage pulse wave may be a DC voltage pulse wave.
  • the period of the DC voltage pulse wave includes two periods.
  • the DC voltage in one of the two periods is, for example, a negative DC voltage, and the potential of the substrate W is set to a negative potential in the one period.
  • the DC voltage level (ie, absolute value) in one of the two periods is higher than the DC voltage level (ie, absolute value) in the other of the two periods.
  • the DC voltage in the other period may be either negative or positive.
  • bias power supply 64 is connected to lower electrode 18 through low pass filter and electrode plate 16 .
  • the pulse wave used as the electrical bias may contain a pulse-like voltage having a waveform other than direct current. Pulsed waves used as electrical biases may include rectangular pulses, triangular pulses, impulses, or pulses of any other waveform. Also, if the pulse wave includes a positive voltage and a negative voltage, the bias power supply 64 may consist of one or more power supplies.
  • the bias power supply 64 may apply a continuous wave of electrical bias to the bottom electrode 18 . That is, the bias power supply 64 may continuously apply an electrical bias to the lower electrode 18 . A continuous wave of electrical bias may be applied to the lower electrode 18 during the period when step STb of method MT is performed.
  • the bias power supply 64 may apply an electrical bias pulse wave to the lower electrode 18 .
  • a pulse wave of electrical bias may be applied to the lower electrode 18 periodically.
  • the period of the electrical bias pulse wave is defined by the third frequency. That is, the time length of the cycle of the electrical bias pulse wave is the reciprocal of the third frequency.
  • the third frequency is lower than the second frequency.
  • the third frequency is, for example, 1 Hz or more and 200 kHz or less. In other examples, the third frequency may be greater than or equal to 5 Hz and less than or equal to 100 kHz.
  • the period of the electrical bias pulse wave includes two periods, ie, the H period and the L period.
  • the level of the electrical bias in the H period (that is, the level of the electrical bias pulse) is higher than the level of the electrical bias in the L period. That is, the electric bias pulse wave may be applied to the lower electrode 18 by increasing or decreasing the level of the electric bias.
  • the level of electrical bias in the L period may be greater than zero.
  • the level of electrical bias during the L period may be zero. That is, the electrical bias pulse wave may be applied to the lower electrode 18 by alternately switching between supplying and stopping the supply of the electrical bias to the lower electrode 18 .
  • the level of the electric bias is the power level of the high frequency power LF.
  • the level of high frequency power LF in the pulses of electrical bias may be 2 kW or more.
  • the level of the electrical bias is the effective value of the absolute value of the negative DC voltage.
  • the duty ratio of the electric bias pulse wave that is, the ratio of the H period in the cycle of the electric bias pulse wave is, for example, 1% or more and 80% or less. In another example, the duty ratio of the electrical bias pulse wave may be 5% or more and 50% or less. Alternatively, the duty ratio of the electric bias pulse wave may be 50% or more and 99% or less.
  • a pulsed wave of electrical bias may be applied to the bottom electrode 18 to perform step STb of method MT.
  • the high frequency power supply 62 may provide a continuous wave of high frequency power HF. That is, the high frequency power supply 62 may continuously supply the high frequency power HF. A continuous wave of high frequency power HF may be supplied during the period when step STb of method MT is being performed.
  • the high frequency power supply 62 may supply a pulse wave of high frequency power HF.
  • a pulsed wave of high frequency power HF may be supplied periodically.
  • the period of the pulse wave of the high frequency power HF is defined by the fourth frequency. That is, the time length of the cycle of the pulse wave of the high frequency power HF is the reciprocal of the fourth frequency.
  • the fourth frequency is lower than the second frequency. In one embodiment, the fourth frequency is the same as the third frequency.
  • the period of the pulse wave of high frequency power HF includes two periods, H period and L period.
  • the power level of the high frequency power HF in the H period is higher than the power level of the high frequency power HF in the L period of the two periods.
  • the power level of the high frequency power HF in the L period may be greater than zero or may be zero.
  • 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 period of the pulse wave of the high frequency power HF may be synchronized with the H period in the period of the pulse wave of the electric 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 electric 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 electric bias.
  • gas is supplied from the gas supply unit to the internal space 10s.
  • a high frequency electric field is generated between the upper electrode 30 and the lower electrode 18 by supplying high frequency power HF and/or an electrical bias.
  • the generated high-frequency electric field generates plasma from the gas in the internal space 10s.
  • the plasma processing apparatus 1 may further include a control section 80 .
  • the control unit 80 may be a computer including a processor, a storage unit such as a memory, an input device, a display device, a signal input/output interface, and the like.
  • the controller 80 controls each part of the plasma processing apparatus 1 .
  • the operator can use the input device to input commands for managing the plasma processing apparatus 1 .
  • the control unit 80 can visualize and display the operation status of the plasma processing apparatus 1 using the display device.
  • the storage unit stores control programs and recipe data.
  • the control program is executed by the processor in order to perform various processes in the plasma processing apparatus 1.
  • FIG. The processor executes a control program and controls each part of the plasma processing apparatus 1 according to recipe data.
  • the method MT will be described by taking as an example the case where it is applied to the substrate W shown in FIG. 2 using the plasma processing apparatus 1 .
  • the control unit 80 controls each unit of the plasma processing apparatus 1 to perform the method MT in the plasma processing apparatus 1 .
  • the control of each unit of the plasma processing apparatus 1 by the control unit 80 for executing the method MT will also be described.
  • FIG. 4 is a partially enlarged cross-sectional view of an exemplary substrate to which the etching method shown in FIG. 1 is applied.
  • step STa a substrate W is prepared in the chamber 10 .
  • the substrate W is placed on and held by the electrostatic chuck 20 within the chamber 10 . It should be noted that the substrate W may have a diameter of 300 mm.
  • step STb is then executed.
  • plasma is generated from the processing gas within the chamber 10 .
  • step STb the film SF is etched by chemical species from plasma. As shown in FIG. 4, the film SF can be etched in step STb until the base region UR is exposed.
  • the processing gas used in step STb contains hydrogen fluoride gas as an etchant gas.
  • the etchant generated from hydrogen fluoride has a small mass, but is excellent in the ability to etch the film SF. Therefore, the selectivity of the etching of the film SF with respect to the etching of the mask MK is increased.
  • the processing gas may or may not contain a rare gas.
  • the flow rate of hydrogen fluoride gas in a process gas that does not contain a noble gas is the highest among all the gas flows in the process gas.
  • the flow rate of the hydrogen fluoride gas in the process gas is the highest among the flow rates of all the gases other than the rare gas in the process gas.
  • the flow rate of the hydrogen fluoride gas in the step STb is 70% by volume or more, 80% by volume or more, and 85% by volume with respect to the total flow rate of the processing gas not containing the rare gas or the processing gas excluding the rare gas. 90% by volume or more, or 95% by volume or more.
  • the flow rate of the hydrogen fluoride gas is It may be less than 100% by volume, 99.5% by volume or less, 98% by volume or less, or 96% by volume or less.
  • 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 processing gas not containing the rare gas or the processing gas excluding the rare gas.
  • the flow rate of the hydrogen fluoride gas in the process gas within such a range, it is possible to etch the film SF at a high etching rate while suppressing the etching of the mask MK.
  • the etching selectivity of the film SF with respect to the etching of the mask MK is a high selectivity of 5 or more.
  • the film SF can be etched at an effective rate even in a process that requires a high aspect ratio, such as a NAND flash memory manufacturing process that has a three-dimensional structure. Moreover, due to such a high selection ratio, the amount of the deposition gas such as the carbon-containing gas to be added can be suppressed, so that the risk of clogging the openings of the mask MK can be reduced.
  • the processing gas used in step STb may further contain a carbon-containing gas. Carbon species generated from the carbon-containing gas deposit on the mask MK to protect it. Therefore, the selectivity of the etching of the film SF with respect to the etching of the mask MK is further enhanced.
  • the carbon-containing gas includes, for example, at least one selected from the group consisting of hydrocarbon (C x H y ) gas, fluorocarbon gas (C v F w ), and hydrofluorocarbon (C s H t Fu ) gas.
  • each of x, y, s, t, u, v, and w is an integer of 1 or more.
  • the carbon-containing gas may contain fluorocarbons and/or hydrofluorocarbons having 1 or more and 6 or less carbon atoms in the molecule. Note that when a carbon-containing gas containing two or more carbon atoms is used, the effect of protecting the side wall surfaces defining the recesses in the mask MK and the film SF can be increased. Further, since hydrogen fluoride is generated from the hydrofluorocarbon gas, the hydrofluorocarbon gas contributes to the improvement of the etching rate of the film SF in addition to the protection of the mask MK by the carbon-containing substance.
  • fluorocarbon gas for example, one or more of CF 4 , C 2 F 2 , C 2 F 4 , C 3 F 8 , C 4 F 6 , C 4 F 8 and C 5 F 8 are used. be able to.
  • Hydrofluorocarbon gases include, for example, CHF 3 , CH 2 F 2 , CH 3 F, C 2 HF 5 , C 2 H 2 F 4 , C 2 H 3 F 3 , C 2 H 4 F 2 , C 3 HF 7 , C3H2F2 , C3H2F6 , C3H2F4 , C3H3F5 , C4H5F5 , C4H2F6 , C5H2F10 , _ _ _ _ _ _ _ _ _
  • One or more of each gas of cC 5 H 3 F 7 and C 3 H 2 F 4 can be used.
  • the hydrocarbon gas for example, one or more of each of CH4 , C2H6 , C3H
  • a fluorocarbon gas with 2 or more carbon atoms and/or a hydrofluorocarbon gas with 2 or more carbon atoms can be used as the carbon-containing gas.
  • a fluorocarbon gas having 2 or more carbon atoms and/or a hydrofluorocarbon gas having 2 or more carbon atoms shape abnormalities such as bowing can be effectively suppressed.
  • a fluorocarbon gas having 3 or more carbon atoms and/or a hydrofluorocarbon gas having 3 or more carbon atoms the shape abnormality can be further suppressed.
  • the fluorocarbon gas having 3 or more carbon atoms for example, C 4 F 8 or C 4 F 6 can be used.
  • the hydrofluorocarbon gas having 3 or more carbon atoms may contain an unsaturated bond and may contain one or more CF 3 groups.
  • As the hydrofluorocarbon gas having 3 or more carbon atoms for example, C 3 H 2 F 4 , C 3 H 2 F 6 or C 4 H 2 F 6 can be used.
  • the processing gas used in step STb may contain a phosphorus-containing gas or an amine-based gas such as NH3 gas.
  • a phosphorus-containing gas or an amine-based gas such as NH3 gas.
  • the presence of phosphorous or amine-based species on the substrate W facilitates the supply of etchant to the bottom of the recess. Therefore, the etching rate of the film SF is increased, and as a result, the selectivity of the etching of the film SF with respect to the etching of the mask MK is increased.
  • the phosphorus species generated from the phosphorus-containing gas also have a protective effect on the sidewalls defining the recesses of the mask MK and film SF.
  • the phosphorus-containing gas contains at least one phosphorus-containing molecule.
  • Phosphorus-containing gases may include oxides such as tetraphosphorus decaoxide ( P4O10 ), tetraphosphorus octaoxide ( P4O8 ), and tetraphosphorus hexaoxide ( P4O6 ). Tetraphosphorus decaoxide is sometimes referred to as diphosphorus pentoxide ( P2O5).
  • Phosphorus-containing gases include phosphorus trifluoride (PF 3 ), phosphorus pentafluoride (PF 5 ), phosphorus trichloride (PCl 3 ), phosphorus pentachloride (PCl 5 ), phosphorus tribromide (PBr 3 ), pentaodorous Halides such as phosphorus chloride (PBr 5 ) and phosphorus iodide (PI 3 ) may be included. That is, the phosphorus-containing gas may contain fluorine or a halogen element other than fluorine as the halogen element.
  • Phosphorus-containing gases may include phosphoryl halides such as phosphoryl fluoride (POF 3 ), phosphoryl chloride (POCl 3 ), phosphoryl bromide (POBr 3 ).
  • Phosphine - containing gas includes phosphine (PH3), calcium phosphide ( Ca3P2 , etc.), phosphoric acid ( H3PO4 ) , sodium phosphate ( Na3PO4 ), hexafluorophosphoric acid ( HPF6 ), etc.
  • Phosphorus-containing gases may include fluorophosphines (H x PF y ). where the sum of x and y is 3 or 5.
  • the phosphorus-containing gas may contain phosphorus fluoride.
  • An example of phosphorus fluoride may include PF3 or PF5 .
  • Examples of fluorophosphines include HPF 2 and H 2 PF 3 .
  • the process gas may contain, as the at least one phosphorus-containing molecule, one or more of the phosphorus-containing molecules described above.
  • the processing gas contains at least one of PF 3 , PCl 3 , PF 5 , PCl 5 , POCl 3 , PH 3 , PBr 3 and PBr 5 as a phosphorus-containing gas. good too.
  • Each phosphorus-containing molecule contained in the process gas can be vaporized by heating or the like and supplied into the chamber 10 if it is liquid or solid.
  • the processing gas used in step STb may contain one or more of NF 3 , O 2 , CO 2 , CO, N 2 , He, Ar, Kr, and Xe.
  • the chemical species produced from these gases can inhibit blockage of openings in the mask MK or increase the verticality of sidewalls of the mask MK.
  • the processing gas used in step STb may contain an oxygen-containing gas.
  • the oxygen-containing gas can include one or more of each of O2 , CO, CO2 , H2O , H2O2.
  • the processing gas used in step STb may contain a halogen-containing gas.
  • the halogen-containing gas suppresses side wall bowing of the film SF.
  • the halogen-containing gas in the process gas used in step STb includes one or more of carbon-free fluorine-containing gas, chlorine-containing gas, bromine-containing gas, and iodine-containing gas.
  • Fluorine-containing gases that do not contain carbon are, for example, SF6, NF3 , XeF2, SiF4 , IF7 , ClF5 , BrF5 , AsF5 , NF5 , PF3 , PF5 , POF3 , BF3 , Contains one or more of each of the gases HPF 6 , WF 6 and the like.
  • the chlorine-containing gas includes one or more of each gas such as Cl2 , HCl, CHxCly , ClF3 , SiCl2 , SiCl4 , CCl4 , BCl3 , PCl3, PCl5 , POCl3 . .
  • x and y are integers of 1 or more.
  • the bromine-containing gas includes one or more of each of Br2, HBr, BrF3 , CBr2F2 , CFxBry , PBr3 , PBr5 , POBr3 , and the like.
  • x and y are integers of 1 or more.
  • CFxBry is, for example , C2F5Br .
  • the iodine-containing gas may include one or more of each of HI, IFt , CxFyIz , I2 , and PI3 .
  • t, x, y, and z are integers of 1 or more.
  • IF t is, for example, IF 5 , IF 7 , and the like.
  • CFxIy is, for example, CF3I , C2F5I , C3F7I , or the like.
  • the iodine-containing gas is CF 3 I gas, for example.
  • the iodine-containing gas can contribute to increasing the verticality of the side wall surfaces of the mask MK in addition to the function of protecting the side walls of the recess.
  • Xe gas having a mass close to that of iodine can also contribute to increasing the verticality of the side wall surface of the mask MK. Therefore, an iodine-containing gas can be used with or in addition to Xe gas.
  • the processing gas may contain WF6 gas instead of or in addition to the iodine - containing gas.
  • the halogen-containing gas in the process gas used in step STb is Cl 2 , Br 2 , HCl, HBr, HI, BCl 3 , CH x Cl y , CF x Br y , CF x I y , ClF 3 , IF 5 , IF 7 and BrF 3 .
  • x and y are integers of 1 or more.
  • the processing gas may further contain an inert gas.
  • Inert gases include nitrogen gas and one or more of various noble gases such as Ar gas, Kr gas, and Xe gas.
  • the control unit 80 controls the gas supply unit to supply the processing gas into the chamber 10 in order to perform the process STb. Further, the control unit 80 controls the gas control unit to set the flow rate of the hydrogen fluoride gas contained in the processing gas to the flow rate described above. Further, the control unit 80 controls the exhaust device 50 to set the pressure of the gas inside the chamber 10 to a specified pressure. Also, the controller 80 controls the plasma generator to generate plasma from the processing gas. In the plasma processing apparatus 1, the controller 80 controls the high frequency power supply 62 and the bias power supply 64 to supply the high frequency power HF, the high frequency power LF, or the high frequency power HF and the electric bias.
  • the step STb may be started after the temperature of the substrate support 14 (especially the electrostatic chuck 20) is set to 0° C. or lower, ⁇ 40° C. or lower, or ⁇ 50° C. or lower. good. Also in the process STb, the temperature of the substrate supporter 14 (especially the electrostatic chuck 20) may be maintained at the temperature before the start of the process STb, or may be changed. When the temperature of the substrate W is set to such a temperature, the etching rate of the film SF in step STb increases.
  • the controller 80 may control the chiller unit to set the temperature of the substrate support 14 .
  • the temperature of the substrate support 14 is 50° C. or less, 30° C. or less, or 20° C. or less depending on the ratio of the phosphorus-containing gas in the processing gas. may be set to
  • the film SF is etched by halogen chemical species from plasma generated from the processing gas.
  • Halogen species include fluorine species generated from hydrogen fluoride gas.
  • Hydrogen fluoride is a molecule with a small molecular weight, and chemical species generated therefrom have a small sputtering effect on the mask MK, thus suppressing etching of the mask MK. Therefore, the plasma generated from the hydrogen fluoride gas can etch the film SF while suppressing the etching of the mask MK.
  • plasma generated from hydrogen fluoride gas can increase the etching rate of the film SF.
  • chemical species generated from the carbon-containing gas protect the mask MK.
  • the plasma generated from the phosphorus-containing gas can suppress etching of the mask MK. Furthermore, in the state where the phosphorus chemical species generated from the phosphorus-containing gas exists on the surface of the substrate W, the supply of the etchant to the bottom of the recess is promoted to increase the etching rate of the film SF. Therefore, according to the method MT, the etching rate is increased in the plasma etching of the film SF, and the selectivity of the etching of the film SF with respect to the etching of the mask MK is increased. Further, when the phosphorus-containing gas contained in the processing gas contains the above-described halogen element and/or when the processing gas contains the above-described halogen-containing gas, the etching rate of the film SF is further increased.
  • phosphorus chemical species are supplied to the substrate W from plasma generated from the phosphorus-containing gas.
  • the phosphorus species may form a protective film on the surface of the substrate W that includes phosphorus.
  • the protective film may further contain carbon and/or hydrogen contained in the process gas.
  • the protective film may further contain oxygen contained in the process gas or contained in the film SF.
  • the protective film may include phosphorus and oxygen bonds.
  • the phosphorus chemical species may form a bond between an element contained in the film SF and phosphorus on the side wall surfaces defining the recesses in the film SF. . If the film SF includes a silicon oxide film, the phosphorus chemical species forms phosphorus-oxygen bonds on the sidewall surfaces of the film SF. In step STb, the sidewall surfaces of film SF are inactivated (or passivated) by phosphorus chemical species. That is, passivation of the sidewall surface of film SF is performed.
  • etching of the side wall surface of the film SF to widen the opening of the film SF in the lateral direction is suppressed.
  • the phosphorus chemical species can form a carbon-phosphorus bond on the surface of the mask MK.
  • the carbon-phosphorus bond has a higher bond energy than the carbon-carbon bond in Mask MK. Therefore, according to the method MT, the mask MK is protected during plasma etching of the film SF.
  • FIG. 5 is an example timing chart for an etching method according to one exemplary embodiment.
  • the horizontal axis indicates time.
  • the vertical axis indicates the power level of the high-frequency power HF, the level of the electrical bias, 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”.
  • a “L” level of the electrical bias indicates that no electrical bias is applied to the lower electrode 18 or that 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 chamber 10
  • the processing gas supply state “OFF” indicates that the processing gas is not being supplied into the chamber 10 . is stopped.
  • a continuous wave of high-frequency power HF may be supplied as indicated by the solid line in FIG. That is, the high-frequency power HF may be continuously supplied during the period in which the step STb is performed.
  • 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.
  • a continuous wave of electrical bias may be applied to the lower electrode 18 as indicated by the solid line in FIG.
  • 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 electrical bias pulse wave described above may be applied to the lower electrode 18 from the bias power supply 64, as indicated by the dashed line in FIG.
  • the electric bias is the high frequency power LF
  • 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 period of the pulse wave of the electric 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 as indicated by the dashed line in FIG.
  • 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 process gas may be supplied and stopped alternately.
  • the period during which the processing gas is supplied may or may not be synchronized with the H period in the cycle of the pulse wave of the high frequency power HF.
  • the period during which the processing gas is supplied may or may not be synchronized with the H period within the cycle of the pulse wave of the electrical bias.
  • FIGS. 6(a), 6(b), 6(c), 7(a), 7(b), 8(a), and 8(b) are an exemplary timing chart of the flow rate of the carbon-containing gas and the pressure within the chamber.
  • (a) of FIG. 7 is a partially enlarged cross-sectional view of an example substrate obtained when the flow rate of the carbon-containing gas is high
  • (b) of FIG. FIG. 4 is a partially enlarged cross-sectional view of an example substrate obtained when not supplied
  • FIG. 8(a) is a partially enlarged sectional view of an example substrate obtained when the pressure in the chamber is high
  • FIG. 8(b) is an example substrate obtained when the pressure in the chamber is low.
  • 1 is a partially enlarged cross-sectional view of FIG.
  • the flow rate of the carbon-containing gas contained in the process gas and/or the pressure within the chamber may be decreased stepwise.
  • the flow rate of the carbon-containing gas contained in the processing gas and/or the pressure in the chamber may be reduced in one step.
  • the flow rate of the carbon-containing gas contained in the processing gas and/or the pressure in the chamber may be reduced in multiple stages.
  • the duration of each step may be the same.
  • the length of time of each step may be different.
  • the flow rate of the carbon-containing gas contained in the processing gas is low or when the carbon-containing gas is not supplied, the amount of carbon-containing deposits DPC formed on the surface of the substrate W is reduced. Therefore, as shown in FIG. 7B, the width of the opening of the mask MK and the width of the bottom of the recess formed in the film SF are increased. However, bowing of the side wall of the film SF may occur and the width of a part of the recess formed in the film SF may be increased.
  • the width of the opening of the mask MK and the film It is possible to suppress the width reduction at the bottom of the concave portion of the SF.
  • the etching rate of the film SF increases.
  • the pressure in the chamber in the step STb is high, as shown in FIG. 8A, the width of the bottom of the recess formed in the film SF may become narrow, resulting in bending of the recess.
  • step (b) the flow rate of the carbon-containing gas contained in the processing gas is may be reduced in stages.
  • the flow rate of the carbon-containing gas contained in the process gas may be reduced stepwise while the pressure in the chamber is set at 2 Pascals (15 mTorr).
  • the film SF was a multi-layer film including alternate lamination of a plurality of silicon oxide films and a plurality of silicon nitride films.
  • the mask MK was made of amorphous carbon.
  • plasma etching was performed on the films SF of eight sample substrates using the plasma processing apparatus 1 .
  • the plasma etching used process gases including fluorocarbon gases, hydrofluorocarbon gases, carbon-free fluorine-containing gases, and halogen-containing gases.
  • the process gas used for plasma etching of the first sample substrate did not contain hydrogen fluoride gas.
  • the flow rates of hydrogen fluoride gas relative to the total flow rate of the processing gases were 34.2% by volume, 51.0% by volume, and 80.0% by volume, respectively. %, 95.2 vol.%, 98.8 vol.%, 99.5 vol.%, and 100 vol.%.
  • the temperature of the electrostatic chuck 20 on which the sample substrate was placed was adjusted to ⁇ 50° C. or less before starting the plasma etching.
  • the etching selectivity of the film SF with respect to the etching of the mask MK was obtained from the plasma etching results of the film SF of eight sample substrates. Specifically, the selectivity was obtained by dividing the etching rate of the film SF by the etching rate of the mask MK from the results of plasma etching of the films SF of eight sample substrates.
  • the results of the first experiment are shown in the graph of FIG.
  • the horizontal axis indicates the flow ratio.
  • the flow rate ratio is the ratio (volume %) of the flow rate of the hydrogen fluoride gas to the total flow rate of the processing gas excluding the rare gas.
  • the vertical axis indicates the selectivity.
  • reference numerals P1 to P8 denote selectivity ratios obtained from plasma etching results of the films SF of the first to eighth sample substrates, respectively.
  • the selection ratio was determined by increasing the ratio of the flow rate of the hydrogen fluoride gas to the total flow rate of the processing gas excluding the rare gas (hereinafter referred to as "flow rate ratio"). It was confirmed that the In particular, in the region where the flow rate ratio is 80 vol% or more, compared to the region where the flow rate ratio is less than 80 vol%, the rate of increase in the selection ratio with respect to the increase in the flow rate ratio is large (the slope of the approximate curve in the graph of FIG. 9 is large) was confirmed. The reason for this is considered as follows. In the region where the flow ratio is less than 80% by volume, the etching rate of the film SF increases as the flow ratio increases, thereby increasing the selectivity.
  • the increase in the selectivity with respect to the increase in the flow rate ratio is relatively moderate.
  • the etching rate of the film SF tends to be saturated, but the etching rate of the mask decreases, thereby increasing the selectivity. That is, in the region where the flow rate ratio is 80% by volume or more, the film SF is etched while maintaining a high etching rate, while the mask is hardly etched. .
  • a selection ratio of 5 or more can be obtained when the flow rate of the hydrogen fluoride gas accounts for 70% by volume or more of the total flow rate of the processing gas excluding the rare gas.
  • the selection ratio is 7 or more, and when it accounts for 95% by volume or more, it is 7.5 or more. can be obtained.
  • the same three sample substrates as the sample substrates used in the first experiment, that is, the ninth to eleventh sample substrates were prepared.
  • plasma etching was performed on the films SF of three sample substrates using the plasma processing apparatus 1 .
  • the plasma etch used a process gas that included hydrogen fluoride gas and a carbon-containing gas.
  • a processing gas containing hydrogen fluoride gas and CH 2 F 2 gas was used for the ninth sample substrate.
  • a process gas containing hydrogen fluoride gas and C 4 F 8 gas was used for the tenth sample substrate.
  • a process gas containing hydrogen fluoride gas and C 4 F 6 H 2 gas was used for the eleventh sample substrate.
  • the temperature of the electrostatic chuck 20 on which the sample substrate was placed was adjusted to ⁇ 50° C. or less before starting the plasma etching.
  • the etching selectivity of the film SF with respect to the etching of the mask MK was obtained from the plasma etching results of the film SF of the three sample substrates. Specifically, the selectivity was obtained by dividing the etching rate of the film SF by the etching rate of the mask MK from the plasma etching results of the films SF of the three sample substrates.
  • the selectivity was 6 or more for any sample substrate.
  • the eleventh sample substrate had a selectivity of about 14, and it was confirmed that the highest selectivity was obtained.
  • the same four sample substrates as the sample substrates used in the first experiment that is, 12th to 15th sample substrates were prepared.
  • plasma etching was performed on the films SF of four sample substrates using the plasma processing apparatus 1 .
  • the plasma etching used a process gas containing hydrogen fluoride gas and C 4 F 8 gas.
  • the process gas used for the twelfth sample substrate contained no other gases.
  • the process gas used for the thirteenth sample substrate contained 10 seem of Cl2 gas.
  • the process gas used for the fourteenth sample substrate contained 10 sccm of HBr gas.
  • the process gas used for the fifteenth sample substrate contained 10 sccm of CF 3 I gas.
  • the pressure in the chamber was 23 mTorr (3.066 Pa) for the plasma etching of the four sample substrates.
  • the high frequency power HF was 40 MHz and 5.5 kW.
  • a pulse wave with a voltage of ⁇ 6 kV was periodically supplied at a frequency of 400 kHz.
  • the plasma etching time for the four sample substrates was 6 minutes.
  • the temperature of the electrostatic chuck 20 on which the sample substrate is placed was adjusted to -70° C. before the plasma etching was started.
  • the width of the recess formed in the film SF was measured at the portion where bowing occurred on the side wall of the film SF.
  • the width of the concave portion of the thirteenth sample substrate was 14 nm smaller than the width of the concave portion of the twelfth sample substrate.
  • the width of the concave portion of the fourteenth sample substrate was 19 nm smaller than the width of the concave portion of the twelfth sample substrate.
  • the width of the concave portion of the fifteenth sample substrate was 42 nm smaller than the width of the concave portion of the twelfth sample substrate.
  • a third experiment result confirmed that sidewall bowing of the film SF was suppressed when the process gas contained a halogen-containing gas such as Cl 2 gas, HBr gas, or CF 3 I gas. It has also been confirmed that bowing of the side walls of the film SF is greatly suppressed when the halogen-containing gas contains iodine having a relatively high mass.
  • a halogen-containing gas such as Cl 2 gas, HBr gas, or CF 3 I gas.
  • the same 16th sample substrate as the sample substrate used in the first experiment was prepared.
  • plasma etching was performed on the film SF of the sixteenth sample substrate using the plasma processing apparatus 1 .
  • the plasma etching used process gases including hydrogen fluoride gas, C 4 F 8 gas, and Xe gas.
  • the pressure in the chamber was 23 mTorr (3.066 Pa).
  • the high frequency power HF was 40 MHz and 5.5 kW.
  • a pulse wave with a voltage of ⁇ 6 kV was periodically supplied at a frequency of 400 kHz.
  • the plasma etching time for the sixteenth sample substrate was 6 minutes.
  • the temperature of the electrostatic chuck 20 on which the sample substrate is placed was adjusted to ⁇ 70° C. before starting the plasma etching.
  • 11(a), 11(b), and 11(c) are cross-sectional photographs of the 12th sample substrate, the 15th sample substrate, and the 16th sample substrate after plasma etching, respectively. .
  • the side surface of the mask MK of the twelfth sample substrate was tapered.
  • the side surfaces of the mask MK had high verticality.
  • the side surface of the mask MK had a high verticality.
  • the plasma processing apparatus 1 was used to generate plasma from a processing gas, which is a mixed gas of hydrogen fluoride gas and argon gas, to etch a silicon oxide film.
  • the plasma processing apparatus 1 was used to generate plasma from a mixed gas of hydrogen fluoride gas, argon gas , and PF3 gas, thereby etching a silicon oxide film.
  • the silicon oxide film was etched while changing the temperature of the electrostatic chuck 20 .
  • a quadrupole mass spectrometer was used to measure the amount of hydrogen fluoride (HF) and the amount of SiF3 in the gas phase during etching of the silicon oxide film.
  • FIG. 12(b) show the results of the fifth experiment and the results of the sixth experiment.
  • FIG. 12(a) shows the relationship between the temperature of the electrostatic chuck 20 and the amounts of hydrogen fluoride (HF) and SiF 3 during etching of the silicon oxide film in the fifth experiment.
  • FIG. 12B shows the relationship between the temperature of the electrostatic chuck 20 and the amounts of hydrogen fluoride (HF) and SiF 3 during etching of the silicon oxide film in the sixth experiment.
  • the amount of etchant consumed in etching the silicon oxide film increased.
  • the process gas used in the sixth experiment differs from the process gas used in the fifth experiment in that it contains PF3 gas. Therefore, in the sixth experiment, a state was formed in which phosphorus chemical species existed on the surface of the silicon oxide film during etching of the silicon oxide film. From this, it was confirmed that the supply of the etchant to the bottom of the recess was promoted and the etching rate of the silicon-containing film was increased when the chemical species of phosphorus existed on the surface of the substrate.
  • the seventh experiment a plurality of sample substrates identical to the sample substrates prepared in the first experiment were prepared.
  • plasma was generated from the processing gas using the plasma processing apparatus 1 to etch the films SF of a plurality of sample substrates.
  • the process gases used in the seventh experiment included hydrogen fluoride gas and fluorocarbon gas.
  • the flow rates of PF3 gas in each of the process gases used for a plurality of sample substrates were different from each other.
  • the ratio of the flow rate of the PF3 gas is the ratio of the flow rate of the PF3 gas to the flow rate of the processing gas.
  • the pressure in the chamber was 27 mTorr (3.6 Pa).
  • the high frequency power HF was 40 MHz and 4.4 kW.
  • a high frequency bias power of 400 kHz and 6 kW was supplied.
  • the duration of the plasma etch for the seventh experiment was 6 minutes.
  • the temperature of the electrostatic chuck 20 on which the sample substrate was placed was adjusted to ⁇ 40° C. before starting the plasma etching.
  • the etching rate of the film SF was obtained from the etching results of the film SF of each of the multiple sample substrates. Then, the relationship between the ratio of the flow rate of the PF 3 gas and the etching rate of the film SF was obtained. The results are shown in FIG. As shown in FIG. 13, it was confirmed that a high etching rate can be obtained if the ratio of the flow rate of the PF3 gas to the flow rate of the processing gas is 2 % or more (or 2.5% or more).
  • the flow rate of the phosphorus-containing gas is 2% or more (or 2.5% or more) with respect to the flow rate of the processing gas containing hydrogen fluoride gas, C 4 F 8 gas, and phosphorus-containing gas (PF 3 gas) It was confirmed that a high etching rate can be obtained if the
  • a plurality of substrates each having a silicon oxide film were prepared.
  • the plasma processing apparatus 1 was used to generate plasma from the processing gas to etch silicon oxide films on a plurality of sample substrates.
  • the temperature of the substrate supporter 14 was different when the silicon oxide films of the sample substrates were etched.
  • a plurality of substrates each having a silicon nitride film were prepared.
  • the plasma processing apparatus 1 was used to generate plasma from the processing gas to etch silicon nitride films on a plurality of sample substrates.
  • the temperature of the substrate supporter 14 was different from each other when etching the silicon nitride films of a plurality of sample substrates.
  • the process gas used in each of the eighth through eleventh experiments included hydrogen fluoride gas and C 4 F 8 gas.
  • the ratio of the PF3 gas flow rate to the process gas flow rate used in the eighth and tenth experiments was 2.5%.
  • the process gas used in the ninth and eleventh experiments did not contain PF3 gas.
  • the other conditions for each of the eighth through eleventh experiments were identical to the corresponding conditions described above for the seventh experiment.
  • the etching rate of the silicon oxide film was obtained from the results of etching the silicon oxide film of each of the plurality of sample substrates.
  • the etching rate of the silicon nitride film was obtained from the etching results of the silicon nitride film of each of the plurality of sample substrates.
  • FIG. 14 shows the relationship between the temperature of the substrate support 14 set in the eighth to eleventh experiments and the obtained etching rate.
  • legend No. 8, No. 9, No. 10, No. 11 refer to the results of the eighth to eleventh experiments, respectively. As shown in FIG.
  • the etching rate of the silicon oxide film was lower than that in the ninth experiment in which the processing gas did not contain PF3 gas. It was confirmed that it was higher than the etching rate. Further, from the result of the eighth experiment, it was found that the etching rate of the silicon oxide film was further increased by setting the temperature of the substrate supporter 14 to 0° C. or less when using the processing gas containing PF3 gas. confirmed.
  • FIG. 15 is a plan view of sample substrates used in the 12th and 13th experiments.
  • the film SF had a laminated structure including a silicon oxide film, a polycrystalline silicon film, and a silicon nitride film.
  • the mask MK was made of amorphous carbon.
  • the mask MK defined multiple openings OP.
  • Each of the plurality of openings OP had a rectangular planar shape, as shown in FIG.
  • the multiple apertures OP were arranged two-dimensionally to provide their multiple rows and multiple columns, as shown in FIG.
  • the process gas was a mixed gas containing H2 gas, Cl2 gas, HBr gas, fluorocarbon gas, hydrofluorocarbon gas , and NF3 gas.
  • the pressure in the chamber was 15 mTorr (2 Pa).
  • the high frequency power HF was 40 MHz and 5.5 kW.
  • high frequency bias power 400 kHz and 7 kW was supplied.
  • the plasma etch time for the twelfth experiment was 1350 seconds.
  • the temperature of the electrostatic chuck 20 on which the sample substrate was placed was adjusted to -35° C. before the plasma etching was started.
  • the process gas was a mixture of hydrogen fluoride gas, PF3 gas , NF3 gas , Cl2 gas, HBr gas, C4F8 gas, and CH2F2 gas.
  • the pressure in the chamber was 25 mTorr (3.066 Pa).
  • the high frequency power HF was 40 MHz and 5.5 kW.
  • a pulse wave with a voltage of ⁇ 6 kV was periodically supplied at a frequency of 400 kHz.
  • the plasma etch time for the thirteenth experiment was 420 seconds.
  • the temperature of the electrostatic chuck 20 on which the sample substrate was placed was adjusted to ⁇ 70° C. before starting the plasma etching.
  • the etching rate of the film SF and the etching selectivity of the film SF with respect to the etching of the mask MK were obtained.
  • the etching rate of the film SF in the thirteenth experiment was approximately three times the etching rate of the film SF in the twelfth experiment.
  • the selectivity in the thirteenth experiment was about 2.5 times the selectivity in the twelfth experiment. Therefore, it was confirmed that the processing gas used in the step STb of the method MT increases the etching rate of the film SF and the etching selectivity of the film SF with respect to the etching of the mask MK.
  • the LER Line Edge Roughness
  • the processing gas used in the step STb of the method MT can suppress deterioration of the shape of the mask MK.
  • the plasma processing apparatus 1 was used to generate plasma from the processing gas to etch the film SF of the sample substrate.
  • the sample substrates used in each of the fourteenth to eighteenth experiments were the same as the sample substrates prepared in the first experiment.
  • the plasma etching used a process gas containing hydrogen fluoride gas.
  • the process gas further included C 4 F 8 gas as a carbon-containing gas.
  • the treatment gas contained no carbon-containing gas.
  • the flow rate of the carbon-containing gas was reduced to 0 sccm in two steps between the start and end of the plasma etch.
  • the flow rate of the carbon-containing gas was decreased to 0 sccm in three steps between the start and end of plasma etching.
  • the flow rate of the carbon-containing gas was decreased to 0 sccm in five steps from the start to the end of plasma etching.
  • the pressure in the chamber was 23 mTorr (3.066 Pa) for the plasma etching of experiments 14-18.
  • the high frequency power HF was 40 MHz and 5.5 kW.
  • a pulse wave with a voltage of ⁇ 6 kV was periodically supplied at a frequency of 400 kHz.
  • the temperature of the electrostatic chuck 20 on which the sample substrate is placed was adjusted to -70° C. before starting the plasma etching.
  • FIG. 16 shows the results of the 14th to 18th experiments.
  • FIG. 16 shows values obtained by standardizing the Bottom CD obtained in each experiment with the Bottom CD obtained in the 14th experiment.
  • FIG. 16 shows values obtained by standardizing the Bow CD obtained in each experiment with the Bow CD obtained in the 14th experiment.
  • FIG. 16 shows values obtained by standardizing the difference obtained in each experiment with the difference obtained in the 14th experiment.
  • the treatment gas did not contain a carbon-containing gas, so the Bottom CD was greater than the Bottom CD in the 14th experiment, but the Bow CD was also greater than the Bow CD in the 14th experiment.
  • the increase in Bow CD was suppressed relative to the Bow CD in the 14th experiment, and the Bottom CD increased relative to the Bottom CD in the 14th experiment.
  • the difference was significantly smaller than the difference in the 14th experiment. Therefore, it was confirmed that by gradually decreasing the flow rate of the carbon-containing gas in the processing gas during plasma etching, it is possible to improve the verticality of the concave portion while suppressing the Bow CD.
  • the plasma processing apparatus 1 was used to plasma-etch the film SF of the same sample substrate as the sample substrate in the first experiment.
  • a mixed gas containing H 2 gas, hydrofluorocarbon gas, fluorocarbon gas, fluorine-containing gas, and halogen-containing gas was used as the process gas for plasma etching.
  • a mixed gas containing hydrogen fluoride gas, C 4 F 8 gas, and O 2 gas was used as the processing gas for plasma etching.
  • the pressure in the chamber was 27 mTorr (3.6 Pa).
  • the high frequency power HF was 40 MHz and 4.4 kW.
  • a high-frequency bias power of 400 kHz and -6 kV was used as an electric bias.
  • the temperature of the electrostatic chuck 20 on which the sample substrate was placed was adjusted to ⁇ 40° C. before starting the plasma etching.
  • the etching rate of the film SF and the etching selectivity of the film SF with respect to the etching of the mask MK were obtained.
  • the etching rates of the film SF in the 20th and 21st experiments were 310 nm/min and 296 nm/min, respectively.
  • the selectivity ratios in the 20th and 21st experiments were 3.24 and 6.52, respectively.
  • the plasma processing apparatus used in the method MT may be a capacitively coupled plasma processing apparatus other than the plasma processing apparatus 1.
  • the plasma processing apparatus used in method MT may be an inductively coupled plasma processing apparatus, an ECR (electron cyclotron resonance) plasma processing apparatus, or a plasma processing apparatus that generates plasma using surface waves such as microwaves. good too.
  • the plasma processing apparatus also includes another bias power supply configured to intermittently or periodically apply voltage pulses to the lower electrode 18. may be provided.
  • a process gas for plasma etching of a silicon oxide film comprising a hydrogen fluoride gas, a phosphorus-containing gas, and a carbon-containing gas.
  • A2 The process gas according to A1, wherein the flow rate of the hydrogen fluoride gas is the highest among the flow rate of the hydrogen fluoride gas, the flow rate of the phosphorus-containing gas, and the flow rate of the carbon-containing gas.
  • B1 A process gas for plasma etching of a silicon oxide film, the process gas comprising a hydrogen fluoride gas, a phosphorus-containing gas, and a carbon-containing gas.
  • the etching method according to B2, wherein the fluorine-containing gas that does not contain carbon is nitrogen trifluoride gas or sulfur hexafluoride gas.
  • B4 The etching method according to any one of B1 to B3, wherein the halogen-containing gas is Cl 2 gas and/or HBr gas.
  • Plasma processing apparatus 10... Chamber, 14... Substrate supporter, 80... Control section, W... Substrate, SF... Film.

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CN202180054563.7A CN116034454A (zh) 2021-04-28 2021-04-28 蚀刻方法
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US18/140,694 US20230268191A1 (en) 2021-04-28 2023-04-28 Etching method
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