WO2020205335A1 - Independent control of etching and passivation gas components for highly selective silicon oxide/silicon nitride etching - Google Patents

Independent control of etching and passivation gas components for highly selective silicon oxide/silicon nitride etching Download PDF

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Publication number
WO2020205335A1
WO2020205335A1 PCT/US2020/024446 US2020024446W WO2020205335A1 WO 2020205335 A1 WO2020205335 A1 WO 2020205335A1 US 2020024446 W US2020024446 W US 2020024446W WO 2020205335 A1 WO2020205335 A1 WO 2020205335A1
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WO
WIPO (PCT)
Prior art keywords
gas
plasma
excited
etching
silicon oxide
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Ceased
Application number
PCT/US2020/024446
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English (en)
French (fr)
Inventor
Du Zhang
Yu-Hao TSAI
Mingmei Wang
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Tokyo Electron Ltd
Tokyo Electron US Holdings Inc
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Tokyo Electron Ltd
Tokyo Electron US Holdings Inc
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Priority to KR1020217034822A priority Critical patent/KR102799165B1/ko
Priority to CN202080024315.3A priority patent/CN113632208B/zh
Priority to JP2021559229A priority patent/JP7545185B2/ja
Publication of WO2020205335A1 publication Critical patent/WO2020205335A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H10P50/244—Dry etching; Plasma etching; Reactive-ion etching of semiconductor materials of Group IV materials comprising alternated and repeated etching and passivation steps
    • 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
    • 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
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
    • H10P14/69215—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material being a silicon oxide, e.g. SiO2
    • 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
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/694—Inorganic materials composed of nitrides
    • H10P14/6943—Inorganic materials composed of nitrides containing silicon
    • H10P14/69433—Inorganic materials composed of nitrides containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz

Definitions

  • the present invention relates to the field of semiconductor manufacturing and semiconductor devices, and more particularly, to a method of selective plasma etching of silicon oxide relative to silicon nitride in semiconductor manufacturing.
  • H2/CH2F2/CH3F/CH4 gases also contributes to etching. Further, many etching methods use only one FC or HFC gas, which provides inadequate flexibility for selectively etching silicon oxide relative to silicon nitride for advanced semiconductor devices. Attempts to fully separate the etching component and the passivation component have not provided full independent control.
  • a method of selective plasma etching of silicon oxide relative to silicon nitride in semiconductor manufacturing is disclosed in several embodiments.
  • the plasma processing method includes providing a substrate containing a silicon oxide film and a silicon nitride film, and selectively etching the silicon oxide film relative to the silicon nitride film by: al) exposing the substrate to a plasma-excited passivation gas containing carbon, sulfur, or both carbon and sulfur, where the passivation gas does not contain fluorine or hydrogen, and bl) exposing the substrate to a plasma-excited etching gas containing a fluorine-containing gas.
  • the plasma processing method includes providing a substrate containing a silicon oxide film and a silicon nitride film, and selectively etching the silicon oxide film relative to the silicon nitride film by: al) exposing the substrate to a plasma-excited passivation gas, wherein the plasma-excited passivation gas includes CO, COS, CS 2 , CCl4, C 2 CI 4 , CCl 2 Br 2 , SC1 2 , S 2 C1 2 , or a combination thereof, and where the passivation gas does not contain fluorine or hydrogen, and bl) exposing the substrate to a plasma-excited etching gas containing F 2 , XeF 2 , C1F 3 , HF, or NF 3 , or a combination thereof.
  • the plasma-excited passivation gas includes CO, COS, CS 2 , CCl4, C 2 CI 4 , CCl 2 Br 2 , SC1 2 , S 2 C1 2 , or a combination thereof
  • the plasma processing method includes providing a substrate containing a silicon oxide film and a silicon nitride film, and selectively etching the silicon oxide film relative to the silicon nitride film by: al) exposing the substrate to a plasma-excited passivation gas, where the plasma excited passivation gas includes CO, COS, CS 2 , CCl4, C 2 Cl4, CCl 2 Br 2 , SC1 2 , or S 2 C1 2 , or a combination thereof, and wherein the passivation gas does not contain fluorine or hydrogen, a2) exposing the substrate to a plasma- excited additional passivation gas containing a fluorocarbon gas, a hydrofluorocarbon gas, a hydrochlorocarbon gas, a hydrochlorofluorocarbon gas, a hydrocarbon gas, or a combination thereof, and bl) exposing the substrate to a plasma -excited etching gas containing F 2 , XeF 2 , C1F 3
  • FIG. 1 is a process flow diagram for selective plasma etching of a silicon oxide film relative to a silicon nitride film according to an embodiment of the invention
  • FIGS. 2A - 2F schematically show through cross-sectional views a method of selective plasma etching of a silicon oxide film relative to a silicon nitride film according to an embodiment of the invention
  • FIG. 3 is a process flow diagram for selective plasma etching of a silicon oxide film relative to a silicon nitride film according to another embodiment of the invention.
  • FIGS. 4A - 4H schematically show through cross-sectional views a method of selective plasma etching of a silicon oxide film relative to a silicon nitride film according to another embodiment of the invention.
  • a method of selective plasma etching of silicon oxide relative to silicon nitride is described.
  • the method utilizes independent control of etching and passivation gas components for highly selective silicon oxide/silicon nitride etching.
  • the inventive selective plasma etching of silicon oxide relative to silicon nitride described in embodiments of the invention fundamentally differs from conventional silicon oxide or silicon nitride etching process by plasmas containing a fluorocarbon (FC) gas or a hydrofluorocarbon (HFC) gas.
  • the passivation gas does not contain fluorine or hydrogen species that contribute to etching, but the passivation gas includes a passivation component (carbon, sulfur, or both carbon and sulfur) that shows sufficient volatility difference on silicon oxide versus silicon nitride.
  • the higher volatility of the passivation component on silicon oxide surfaces is thought to be due to the“closed-shell” nature (no unpaired electrons) of carbon by-products on the silicon oxide surfaces, compared to“open-shell” nature (unpaired electrons) of carbon by-products on the silicon nitride surfaces.
  • sulfur-containing etch by-products are thought to be volatile on silicon oxide surfaces but involatile as polymers on silicon nitride surfaces.
  • the etching component is provided using a fluorine -containing gas.
  • the fluorine-containing gas does not contain a fluorocarbon gas or a hydrofluorocarbon gas. This full separation of the passivation component and the etching component greatly enhances the processing window and the etch selectivity between silicon oxide and silicon nitride.
  • FIG. 1 is a process flow diagram for selective plasma etching of a silicon oxide film relative to a silicon nitride film according to an embodiment of the invention
  • FIGS. 2A - 2F schematically show through cross-sectional views a method of selective plasma etching of a silicon oxide film relative to a silicon nitride film according to an embodiment of the invention.
  • the plasma processing method 10 includes, in 12, providing a substrate 1 containing a silicon oxide film 200 (e.g., Si0 2 ) and a silicon nitride film 220 (e.g., S1 3 N 4 ).
  • a silicon oxide film 200 e.g., Si0 2
  • a silicon nitride film 220 e.g., S1 3 N 4
  • Si 3 N is the most thermodynamically stable of the silicon nitrides and hence the most commercially important of the silicon nitrides.
  • embodiments of the invention may be applied to other silicon nitrides that contain Si and N as the major constituents, where the silicon nitrides can have a wide range of Si and N compositions.
  • Si0 2 is the most thermodynamically stable of the silicon oxides and hence the most commercially important of the silicon oxides.
  • embodiments of the invention may be applied to other silicon oxides that contain Si and O as the major constituents, where the silicon oxides can have a wide range of Si and O compositions.
  • the method further includes, in 14, exposing the substrate 1 to a plasma-excited passivation gas 201 containing carbon, sulfur, or both carbon and sulfur, where the plasma- excited passivation gas 201 does not contain fluorine or hydrogen.
  • a plasma-excited passivation gas 201 gas can include CO, COS, CS 2 , CCI 4 , C 2 C1 , CCl 2 Br 2 , SC1 2 , or S 2 C1 2 , or a combination thereof.
  • the exposure to the plasma-excited passivation gas 201 forms a passivation layer 222 on the substrate 2 as shown in FIG. 2C.
  • the passivation layer 222 is thicker on the silicon nitride film 220 than on the silicon oxide film 200 due to the higher volatility of the by-products of the plasma-excited passivation gas 201 on the silicon oxide film 200 than on the silicon nitride film 220.
  • the method further includes, in 16, exposing the substrate to a plasma -excited etching gas 203 containing a fluorine-containing gas.
  • plasma-excited etching gas 203 includes F 2 , XeF 2 , C1F 3 , HF, NF 3 , or a combination thereof.
  • the plasma-excited etching gas can optionally further include Ar, He, or a combination thereof.
  • the fluorine-containing gas does not contain a fluorocarbon gas or a hydrofluorocarbon gas.
  • the exposure to the plasma- excited etching gas 203 selectively etches the silicon oxide film 200 relative to the silicon nitride film 220 due to the thicker passivation layer 222 on the silicon nitride film 220 than on the silicon oxide film 200.
  • the selective etching is schematically shown in FIG. 2E, where the passivation layer 222 is removed from the silicon oxide film 200 and the silicon oxide film 200 is etched, while the passivation layer 222 on the silicon nitride film 220 is thinned but protects the silicon nitride film 220 from etching.
  • the exposing steps 14 and 16 may be performed alternatively and sequentially. Further, as shown by the process arrow 18, the exposing steps 14 and 16 may be repeated at least once to further selectively etch the silicon oxide film 100. According to one embodiment, the exposing steps 14 and 16 may at least partially overlap in time.
  • the method can further include removing the passivation layer 222 from the substrate 2 using an ashing process following the etching process. This is schematically shown in FIG. 2F.
  • FIG. 3 is a process flow diagram for selective plasma etching of a silicon oxide film relative to a silicon nitride film according to an embodiment of the invention
  • FIGS. 4A - 4H schematically show through cross-sectional views a method of selective plasma etching of a silicon oxide film relative to a silicon nitride film according to another embodiment of the invention.
  • the plasma processing method 30 includes, in 32, providing a substrate 4 containing a silicon oxide film 400 and a silicon nitride film 420.
  • the silicon oxide film 400 and the S1 3 N 4 film 420 are in the same horizontal plane, but embodiments of the invention may also be applied to films that are not in the same horizontal plane but are offset vertically.
  • the method further includes, in 34, exposing the substrate 4 to a plasma-excited passivation gas 401 containing carbon, sulfur, or both carbon and sulfur, where the passivation gas does not contain fluorine or hydrogen.
  • a plasma-excited passivation gas 401 containing carbon, sulfur, or both carbon and sulfur, where the passivation gas does not contain fluorine or hydrogen.
  • the plasma-excited passivation gas 401 can include CO, COS, CS 2 ,
  • the exposure to the plasma- excited passivation gas 401 forms a passivation layer 422 on the substrate 4 as shown in FIG. 4C.
  • the passivation layer 422 is thicker on the silicon nitride film 420 than on the silicon oxide film 400 due to the higher volatility of the by-products of the plasma-excited passivation gas 401 on the silicon oxide film 400 than on the silicon nitride film 420.
  • the method further includes, in 36, exposing the substrate 4 to a plasma-excited additional passivation gas 423 containing a fluorocarbon gas, a hydrofluorocarbon gas, a hydrochlorocarbon gas, a hydrochlorofluorocarbon gas, a hydrocarbon gas, or a combination thereof.
  • the plasma-excited additional passivation gas can contain CF 2 C1 2 , CH 2 F 2 , CH 4 , CH 3 F, CHF S , C 4 H 6 , C 2 H 4 , C 3 H 6 , CH 2 C1 2 , CH 3 C1, CH 3 C1, CH 2 C1F, CHC1 2 F, or a combination thereof.
  • the exposure to the plasma-excited additional passivation gas 423 forms an enhanced passivation layer 424 on the substrate 4 as shown in FIG. 4E.
  • the exposure to the plasma-excited additional passivation gas 423 is used for modifying and strengthening the passivation layer 422 without damaging the underlying silicon nitride film 420, since the passivation layer 422 protects the underlying silicon nitride film 420 during the plasma exposure.
  • the exposure to the plasma-excited additional passivation gas 423 may be performed using low or zero substrate bias to avoid damaging of the silicon nitride film 420 by fluorine or hydrogen ions and/or radicals in the plasma.
  • the method further includes, in 38, exposing the substrate 4 to a plasma-excited etching gas 403 containing a fluorine-containing gas. This is schematically shown in FIG.
  • plasma-excited etching gas 403 includes F 2 , XeF 2 , C1F 3 , HF, NF 3 , or a combination thereof.
  • the plasma-excited etching gas can optionally further include Ar, He, or a combination thereof.
  • the fluorine-containing gas does not contain a fluorocarbon gas or a hydrofluorocarbon gas. The exposure to the plasma-excited etching gas 402 selectively etches the silicon oxide film 400 relative to the silicon nitride film 420 as shown in FIG. 4G.
  • the exposure to the plasma-excited etching gas 403 selectively etches the silicon oxide film 400 relative to the silicon nitride film 420 due to the thicker enhanced passivation layer 424 on the silicon nitride film 420 than on the silicon oxide film 400.
  • the selective etching is schematically shown in FIG. 4G, where the enhanced passivation layer 424 is removed from the silicon oxide film 400 and the silicon oxide film 400 is etched, while the enhanced passivation layer 424 on the silicon nitride film 420 is thinned but protects the silicon nitride film 420 from etching.
  • the exposing steps 34 - 38 may performed alternatively and sequentially.
  • the exposing steps 34 - 38 may be performed alternatively and sequentially in the order: 34, followed by 36, and followed by 38. Further, as shown by the process arrow 40, the exposing steps 34 - 38 may be repeated at least once to further selectively etch the silicon oxide film 400. According to one embodiment, one or more of the exposing steps 34 - 38 may at least partially overlap in time.
  • the method can further include removing the enhanced passivation layer 424 from the substrate 4 using an ashing process following the etching process. This is schematically shown in FIG. 4H.
  • the method of selective plasma etching of silicon oxide films relative to silicon nitride films may be performed in conventional commercial plasma processing systems, including Inductively Coupled Plasma (ICP) systems, Capacitively Coupled Plasma (CCP) systems, microwave plasma systems, remote plasma systems that generate plasma excited species upstream from the substrate, electron cyclotron resonance (ECR) systems, and other systems.
  • ICP Inductively Coupled Plasma
  • CCP Capacitively Coupled Plasma
  • microwave plasma systems remote plasma systems that generate plasma excited species upstream from the substrate
  • ECR electron cyclotron resonance
  • the selective silicon oxide/silicon nitride etching process may be performed at substrate temperatures, gas flows, gas flow ratios, and gas pressures that optimize etch selectivity between silicon oxide and silicon nitride. Examples include a substrate temperatures, gas flows, gas flow ratios, and gas pressures that optimize etch selectivity between silicon oxide and silicon nitride. Examples include a substrate temperatures, gas flows, gas flow ratios, and gas pressures that optimize etch selectivity between silicon oxide and silicon nitride. Examples include a substrate temperatures, gas flows, gas flow ratios, and gas pressures that optimize etch selectivity between silicon oxide and silicon nitride. Examples include a substrate temperatures, gas flows, gas flow ratios, and gas pressures that optimize etch selectivity between silicon oxide and silicon nitride. Examples include a substrate temperatures, gas flows, gas flow ratios, and gas pressures that optimize etch selectivity between silicon oxide and silicon nitride. Examples include a substrate temperatures, gas flows, gas flow ratios, and gas pressures that optimize
  • the gas pressure in the plasma etch chamber can between about 5mTorr and about lOOOmTorr, between about lOmTorr and 500mTorr, or between about 20mTorr and about lOOmTorr. Examples of gas flows are from 0.1 seem to 500 seem, with flow ratio of any gas from 0 % to 100 %.

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PCT/US2020/024446 2019-04-05 2020-03-24 Independent control of etching and passivation gas components for highly selective silicon oxide/silicon nitride etching Ceased WO2020205335A1 (en)

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Application Number Priority Date Filing Date Title
KR1020217034822A KR102799165B1 (ko) 2019-04-05 2020-03-24 고도로 선택적인 실리콘 산화물/실리콘 질화물 에칭을 위한 에칭 가스 성분과 패시베이션 가스 성분의 독립적 제어
CN202080024315.3A CN113632208B (zh) 2019-04-05 2020-03-24 用于高度选择性氧化硅/氮化硅蚀刻的蚀刻和钝化气体组分的独立控制
JP2021559229A JP7545185B2 (ja) 2019-04-05 2020-03-24 高度に選択的な酸化ケイ素／窒化ケイ素エッチングのためのエッチング成分及び不動態化ガス成分の独立した制御

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US201962830223P 2019-04-05 2019-04-05
US62/830,223 2019-04-05

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JP (1) JP7545185B2 (https=)
KR (1) KR102799165B1 (https=)
CN (1) CN113632208B (https=)
TW (1) TWI874377B (https=)
WO (1) WO2020205335A1 (https=)

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JP7545185B2 (ja) 2024-09-04
CN113632208B (zh) 2025-11-18
KR102799165B1 (ko) 2025-04-21
TW202104659A (zh) 2021-02-01
CN113632208A (zh) 2021-11-09
US20200321218A1 (en) 2020-10-08
TWI874377B (zh) 2025-03-01
JP2022527552A (ja) 2022-06-02
US11024508B2 (en) 2021-06-01

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