WO2024019123A1 - 炭素原子含有膜のドライエッチング方法 - Google Patents

炭素原子含有膜のドライエッチング方法 Download PDF

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Publication number
WO2024019123A1
WO2024019123A1 PCT/JP2023/026645 JP2023026645W WO2024019123A1 WO 2024019123 A1 WO2024019123 A1 WO 2024019123A1 JP 2023026645 W JP2023026645 W JP 2023026645W WO 2024019123 A1 WO2024019123 A1 WO 2024019123A1
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Prior art keywords
carbon atom
containing film
etching
mask
opening
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Ceased
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PCT/JP2023/026645
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English (en)
French (fr)
Japanese (ja)
Inventor
勝 堀
健治 石川
ティ トゥイ ガー グエン
優太 青木
修司 津野
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Sumitomo Seika Chemicals Co Ltd
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Sumitomo Seika Chemicals Co Ltd
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Priority to CN202380037841.7A priority Critical patent/CN119137715A/zh
Priority to JP2024535136A priority patent/JPWO2024019123A1/ja
Publication of WO2024019123A1 publication Critical patent/WO2024019123A1/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • 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

Definitions

  • the present disclosure relates to a method of dry etching a film containing carbon atoms.
  • Patent Document 1 has room for improvement in that when dry etching the carbonaceous layer, the carbonaceous layer is anisotropically etched preferentially over the mask placed on the carbonaceous layer. It had Here, if the etching rate for the mask placed on the carbonaceous layer is higher than the etching rate for the carbonaceous layer, it may be possible to increase the thickness of the mask. However, in that case, there was a risk that the mask would collapse due to etching.
  • An object of the present invention is to provide a method for dry etching a carbon atom-containing film.
  • the inventors of the present disclosure have arranged a mask containing an oxygen-containing material as a mask disposed on a carbon atom-containing film, and while setting the opening width of the mask to a specific range, the oxygen content during etching of the carbon atom-containing film is By changing the gas added to carbonyl sulfide from sulfur dioxide, we surprisingly found that the above problems could be solved, leading to the present disclosure.
  • one aspect of the present disclosure is a dry etching method for a carbon atom-containing film, the method comprising etching a carbon atom-containing film with an etching gas, the method comprising using a mixed gas containing at least oxygen and sulfur dioxide as a carbon atom-containing film.
  • the carbon atom-containing film when dry etching a carbon atom-containing film, is preferentially etched anisotropically over a mask placed on the carbon atom-containing film. Can be done.
  • the width of the first opening of the mask may be 40 to 150 nm.
  • the shape of the first opening may be a trench or a hole.
  • the carbon atom-containing film may include amorphous carbon.
  • the oxygen-containing material included in the mask may be silicon dioxide.
  • the thickness of the carbon atom-containing film may be 0.1 ⁇ m or more.
  • the thickness of the carbon atom-containing film may be 10.0 ⁇ m or less.
  • the thickness of the mask may be 0.01 times or more the thickness of the carbon atom-containing film.
  • the thickness of the mask may be 0.5 times or less the thickness of the carbon atom-containing film.
  • the content of the sulfur dioxide in the total volume of the sulfur dioxide and the oxygen may be 20 to 40% by volume.
  • the carbon atom-containing film when dry etching a carbon atom-containing film, can be anisotropically etched preferentially over a mask placed on the carbon atom-containing film.
  • a dry etching method is provided.
  • FIG. 2 is a cross-sectional view showing an example of a structure before an etching step in the dry etching method for a carbon atom-containing film according to the present disclosure.
  • FIG. 2 is a schematic diagram showing an etching chamber in which the structure of FIG. 1 is placed.
  • FIG. 2 is a cross-sectional view showing an example of a structure after an etching step of the dry etching method for a carbon atom-containing film according to the present disclosure.
  • 4 is a partially enlarged view of the mask and carbon atom-containing film of FIG. 3.
  • FIG. 3 is a graph showing the results of plotting the etching selectivity against the trench design width of the mask in Examples 1 to 3 and Comparative Examples 1 to 3.
  • FIG. 1 is a cross-sectional view showing an example of a structure before the etching process of the dry etching method for a carbon atom-containing film of the present disclosure
  • FIG. 2 is a schematic diagram showing an etching chamber in which the structure shown in FIG. 1 is arranged.
  • 3 is a cross-sectional view showing an example of a structure after the etching process of the dry etching method for a carbon atom-containing film of the present disclosure
  • FIG. 4 is a partially enlarged view of the carbon atom-containing film in FIG.
  • the method of dry etching a carbon atom-containing film is a method of etching a carbon atom-containing film 20 containing carbon atoms with an etching gas, in which a mixed gas G containing at least oxygen and sulfur dioxide is applied to the carbon atom-containing film 20. , and a step of introducing a mixed gas into the etching chamber 1 in which the structure 100 including the mask 30 having the first opening 31 is arranged, and converting the mixed gas G into plasma in the etching chamber 1 to generate plasma gas. , and an etching step of etching the carbon atom-containing film 20 of the structure 100 using this plasma gas to form the second opening 21 (see FIGS. 1 to 3).
  • the mask 30 includes an oxygen-containing material, and the width L1 of the first opening 31 of the mask 30 is 10 to 150 nm.
  • the mask 30 placed on the carbon atom-containing film 20 during etching includes an oxygen-containing material, and the width L1 of the first opening 31 of the mask 30 is specified.
  • the structure 100 includes a carbon atom-containing film 20 containing carbon atoms, and a mask 30 having a first opening 31.
  • the structure 100 may further include a support 10 that supports the carbon atom-containing film 20, as shown in FIG. In this case, the carbon atom-containing film 20 is placed between the mask 30 and the support 10. Further, the structure 100 may further include an intermediate film (not shown) between the support body 10 and the carbon atom-containing film 20.
  • the support body 10 is not particularly limited as long as it is a member that supports the carbon atom-containing film 20, examples of the material constituting the support body 10 include silicon, germanium, and the like. Among them, silicon is preferred. In this case, since the bandgap is wide, durability under high pressure is further improved.
  • the thickness of the support 10 is not particularly limited, but may be 254 ⁇ m or more, or 520 ⁇ m or more. When the thickness of the support 10 is 254 ⁇ m or more, the mechanical strength is further improved. Moreover, the thickness of the support body 10 may be 795 ⁇ m or less, or may be 725 ⁇ m or less. When the thickness of the support 10 is 795 ⁇ m or less, the structure 100 can be easily cut into wafers of a predetermined size.
  • intermediate film examples include silica (SiO 2 ), silicon nitride (Si 3 N 4 ), amorphous silicon (a:Si), and polycrystalline silicon (poly:Si).
  • the carbon atom-containing film 20 is not particularly limited as long as it contains carbon atoms.
  • the carbon atom-containing film 20 may be an inorganic carbon film such as amorphous carbon, or may be an organic polymer film such as a resist film or a polyimide film.
  • the etching selectivity i.e., the ratio of the etching speed Vc of the carbon atom-containing film to the etching speed Vm of the mask
  • the etching selectivity is increased when transferring the pattern to the carbon atom-containing film 20. Can be done.
  • the thickness of the carbon atom-containing film 20 is not particularly limited, but may be 0.1 ⁇ m or more, or 0.5 ⁇ m or more. When the thickness of the carbon atom-containing film 20 is 0.1 ⁇ m or more, if an intermediate film is laminated as a layer to be etched under the carbon atom-containing film 20, the carbon atom-containing film 20 can act as a mask for the layer to be etched. It becomes possible to demonstrate the functions of Further, the thickness of the carbon atom-containing film 20 may be 10 ⁇ m or less, or 5 ⁇ m or less. When the thickness of the carbon atom-containing film 20 is 10 ⁇ m or less, the carbon atom-containing film 20 becomes difficult to collapse after etching.
  • the mask 30 has a first opening 31 that allows the etching gas to pass through and guide it to the carbon atom-containing film 20 .
  • the shape of the first opening 31 is not particularly limited, and may be a trench or a hole, for example.
  • Mask 30 includes an oxygen-containing material.
  • the etching rate for the mask 30 can be made relatively slower than the etching rate for the carbon atom-containing film 20, and when dry etching the carbon atom-containing film 20,
  • the carbon atom-containing film 20 can be anisotropically etched more preferentially than the mask 30.
  • the oxygen-containing material include silicon dioxide and silicon oxynitride. Among them, silicon dioxide is preferred from the viewpoint of economy.
  • the width L1 of the first opening 31 is a designed width of the first opening 31, and the width L1 of the first opening 31 is 10 to 150 nm.
  • the width L1 of the first opening 31 is 10 nm or more, the generated plasma can easily etch the carbon atom-containing film 20. Since the width L1 of the first opening 31 is 150 nm or less, when dry etching the carbon atom-containing film 20, the carbon atom-containing film 20 is given priority over the mask 30 disposed on the carbon atom-containing film 20. Can be anisotropically etched.
  • the width L1 of the first opening 31 may be 40 to 150 nm, 50 to 150 nm, or 60 to 100 nm.
  • the thickness of the mask 30 is not particularly limited, but may be 0.01 times or more, or 0.1 times or more, the thickness of the carbon atom-containing film 20. When the thickness of the mask 30 is 0.01 times or more the thickness of the carbon atom-containing film 20, anisotropic etching of the carbon atom-containing film becomes possible. Further, the thickness of the mask 30 may be 0.5 times or less, or 0.2 times or less, the thickness of the carbon atom-containing film 20. When the thickness of the mask 30 is 0.5 times or less than the thickness of the carbon atom-containing film 20, the carbon atom-containing film 20 becomes difficult to collapse after etching.
  • the etching chamber 1 is a container in which the carbon atom-containing film 20 is etched by a plasma gas in which a mixed gas G containing oxygen and sulfur dioxide is turned into plasma, and constitutes a part of an etching apparatus.
  • etching equipment include microwave ECR plasma etching equipment, capacitively coupled plasma (CCP) etching equipment, and inductively coupled plasma (ICP) etching equipment, but etching equipment is not limited to these. It's not something you can do.
  • Mixed gas G contains oxygen and sulfur dioxide.
  • the content of sulfur dioxide in the total volume of oxygen and sulfur dioxide is not particularly limited as long as it is larger than 0% by volume, but may be 20 to 40% by volume, or may be 25 to 35% by volume. .
  • the etching rate for the carbon atom-containing film 20 can be more effectively improved.
  • the flow rate of the mixed gas G when introduced into the etching chamber 1 may be 0.1 mL/min or more, 1 mL/min or more, or 10 mL/min or more.
  • the flow rate of the mixed gas G when introduced into the etching chamber 1 may be 10000 mL/min or less, 1000 mL/min or less, or 100 mL/min or less.
  • the degree of vacuum in the etching apparatus can be easily maintained at a low pressure.
  • the mixed gas G is turned into plasma in the etching chamber 1 to generate plasma gas, and the carbon atom-containing film 20 of the structure 100 is etched using this plasma gas to form the second opening 21. It is a process.
  • the structure 100 becomes a structure 200 through the etching process.
  • the pressure inside the etching chamber 1 during dry etching may be between 0.1 mTorr and 100 mTorr, and may also be between 0.1 mTorr and 100 mTorr. When the pressure inside the etching chamber 1 is between 0.1 mTorr and 100 mTorr, the pressure is low, so it becomes possible to perform excellent shape control on the second opening 21.
  • the antenna power is not particularly limited, but may be 50 to 1000 W, or 100 to 800 W. It may be 200 to 600W. By setting the antenna power to 50 to 1000 W, the carbon atom-containing film 20 can be etched at high speed and anisotropically.
  • ICP inductively coupled plasma
  • bias power When an inductively coupled plasma (ICP) etching device is used as the etching device, the bias power is not particularly limited, but may be 10 W or more, 25 W or more, 50 W or more. It may be. By setting the bias power to 10 W or more, it becomes easier to increase the aspect ratio of the second opening 21. Further, the bias power may be 500W or less, 300W or less, or 200W or less. By setting the bias power to 500 W or less, it becomes easier to appropriately control dry etching.
  • ICP inductively coupled plasma
  • the shape of the second opening 21 of the carbon atom-containing film 20 after etching is the same as the shape of the first opening 31. That is, when the first opening 31 is a trench, the second opening 21 is also a trench, and when the first opening 31 is a hole, the second opening 21 is also a hole.
  • the aspect ratio of the second opening 21 of the carbon atom-containing film 20 after etching is not particularly limited, but may be, for example, 0.1 to 60, 1 to 40, or 4 to 40. It may be 5 to 40, or 5 to 25.
  • the etching rate for the carbon atom-containing film 20 can be improved compared to the case where the carbon atom-containing film 20 is etched with a plasma gas of the mixed gas G containing oxygen and carbonyl sulfide. .
  • the aspect ratio is 0.1 or more, so that, for example, the carbon atom-containing film 20 is It becomes more effective as a mask.
  • the lower layer include silica (SiO 2 ), silicon nitride (Si 3 N 4 ), amorphous silicon (a:Si), and polycrystalline silicon (poly:Si).
  • the aspect ratio refers to the ratio (L2/L1) of the depth (L2) of the second opening 21 to the designed width (L1) of the first opening 31 in the cross section of the carbon atom-containing film 20.
  • the design width L1 of the first opening 31 refers to the length of the first opening 31 along the interface between the carbon atom-containing film 20 and the mask 30 in the cross section of the mask 30.
  • the cross section of the mask 30 is a cross section taken along a plane perpendicular to the longitudinal direction of the trench and along the thickness direction of the mask 30.
  • the depth of the second opening 21 is the length from the interface between the carbon atom-containing film 20 and the mask 30 to the bottom surface of the second opening 21 in the cross section of the carbon atom-containing film 20. 20 along the thickness direction.
  • Analytical instruments for confirming etching performance include SEM (scanning electron microscope) and TEM (transmission electron microscope), but analytical instruments are particularly limited as long as they are capable of confirming etching speed and occurrence of bowing. It's not a thing.
  • a method for dry etching a carbon atom-containing film which comprises etching a carbon atom-containing film with an etching gas, wherein a mixed gas containing at least oxygen and sulfur dioxide is etched into the carbon atom-containing film and the carbon atom-containing film. a step of introducing a mixed gas into an etching chamber in which a structure including a mask having one opening is placed; a step of introducing a mixed gas into an etching chamber in which a structure including a mask having one opening; a plasma gas is generated by converting the mixed gas into plasma in the etching chamber; and the plasma gas is used in the etching process.
  • [4] The method of dry etching a carbon atom-containing film according to any one of [1] to [3], wherein the carbon atom-containing film contains amorphous carbon.
  • [5] The method for dry etching a carbon atom-containing film according to any one of [1] to [4], wherein the oxygen-containing material contained in the mask is silicon dioxide.
  • [6] The method for dry etching a carbon atom-containing film according to any one of [1] to [5], wherein the thickness of the carbon atom-containing film is 0.1 ⁇ m or more.
  • Example 1 First, a laminate consisting of a Si substrate as a support and an amorphous carbon film (thickness: about 2400 nm) as a carbon atom-containing film was prepared. Then, on the amorphous carbon film of this laminate, a mask pattern as a first opening is formed by lithography, and a silicon dioxide film having a silicon film as an underlying layer (total thickness of silicon film and silicon dioxide film: approx. 350 nm) was placed as a mask, and a 20 mm square structure was prepared (see FIG. 1).
  • the mask pattern of the mask is a trench pattern
  • the trench design width (design width of the first opening) L1 is 60 nm
  • the mask design width (width of the actual part of the mask other than the first opening) W is 240 nm.
  • ICP inductively coupled plasma
  • dry etching of the amorphous carbon film was performed as follows. That is, the vacuum pressure in the etching chamber was set to 3.8 mTorr, the antenna power was set to 400 W, and the bias power was set to 100 W, and a mixed gas was introduced into the etching chamber at a flow rate of 50 mL/min to generate plasma gas as an etching gas. The amorphous carbon film was dry etched using this plasma gas to form a trench pattern as a second opening in the amorphous carbon film. In this way, dry etching of the carbon atom-containing film was completed.
  • the mixed gas is composed of a mixed gas of oxygen and sulfur dioxide
  • the etching time is 20 minutes
  • the content of sulfur dioxide in the total volume of oxygen and sulfur dioxide is 30% by volume (the content of oxygen is 70% by volume).
  • the cross section of the amorphous carbon film was observed using a SEM (product name "SU8230", manufactured by Hitachi High-Tech Corporation), and the etching depth (L2) of the trench pattern formed in the amorphous carbon film was confirmed.
  • the length L2 was 1706 nm
  • the etching rate Vc of the carbon film was 85 nm/min as shown in Table 1.
  • the depth was 179 nm
  • the etching rate Vm of the mask was 8. It was 7 nm/min.
  • Example 1 Dry etching of the amorphous carbon film was performed in the same manner as in Example 1 except that the mixed gas was as shown in Table 1. Then, the etching rates of the carbon atom-containing film and the mask were calculated. The results are shown in Table 1. As shown in Table 1, the etching rate Vc of the carbon atom-containing film was 74 nm/min, the etching rate Vm of the mask was 11.4 nm/min, and the etching selectivity (Vc/Vm) was 6.
  • Example 2 Dry etching of the amorphous carbon film was performed in the same manner as in Example 1 except that the trench design width L1 and the mask design width W of the mask were as shown in Table 2. Then, the etching rates of the carbon atom-containing film and the mask were calculated. The results are shown in Table 2. As shown in Table 2, the etching rate Vc of the carbon atom-containing film was 105 nm/min, the etching rate Vm of the mask was 7.4 nm/min, and the etching selectivity (Vc/Vm) was 14.
  • Example 3 Dry etching of the amorphous carbon film was performed in the same manner as in Example 1 except that the trench design width L1 and the mask design width W of the mask were as shown in Table 2. Then, the etching rates of the carbon atom-containing film and the mask were calculated. The results are shown in Table 3. As shown in Table 3, the etching rate Vc of the carbon atom-containing film was 116 nm/min, the etching rate Vm of the mask was 5.4 nm/min, and the etching selectivity (Vc/Vm) was 21.
  • Example 3 Dry etching of the amorphous carbon film was performed in the same manner as in Example 3 except that the mixed gas was as shown in Table 3. Then, the etching rates of the carbon atom-containing film and the mask were calculated. The results are shown in Table 3. As shown in Table 3, the etching rate Vc of the carbon atom-containing film was 98 nm/min, the etching rate Vm of the mask was 6.5 nm/min, and the etching selectivity (Vc/Vm) was 15.

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PCT/JP2023/026645 2022-07-22 2023-07-20 炭素原子含有膜のドライエッチング方法 Ceased WO2024019123A1 (ja)

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CN202380037841.7A CN119137715A (zh) 2022-07-22 2023-07-20 含碳原子膜的干式蚀刻方法
JP2024535136A JPWO2024019123A1 (https=) 2022-07-22 2023-07-20

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008512002A (ja) * 2004-09-02 2008-04-17 マイクロン テクノロジー，インコーポレイテッド ピッチ増倍を使用する集積回路の製造方法
JP2012204668A (ja) * 2011-03-25 2012-10-22 Tokyo Electron Ltd プラズマエッチング方法および記憶媒体
US20170125260A1 (en) * 2015-11-04 2017-05-04 Lam Research Corporation Methods and Systems for Advanced Ion Control for Etching Processes
JP2018200925A (ja) * 2017-05-25 2018-12-20 東京エレクトロン株式会社 エッチング方法およびエッチング装置
US20220189781A1 (en) * 2020-12-11 2022-06-16 Tokyo Electron Limited Non-Atomic Layer Deposition (ALD) Method of Forming Sidewall Passivation Layer During High Aspect Ratio Carbon Layer Etch

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008512002A (ja) * 2004-09-02 2008-04-17 マイクロン テクノロジー，インコーポレイテッド ピッチ増倍を使用する集積回路の製造方法
JP2012204668A (ja) * 2011-03-25 2012-10-22 Tokyo Electron Ltd プラズマエッチング方法および記憶媒体
US20170125260A1 (en) * 2015-11-04 2017-05-04 Lam Research Corporation Methods and Systems for Advanced Ion Control for Etching Processes
JP2018200925A (ja) * 2017-05-25 2018-12-20 東京エレクトロン株式会社 エッチング方法およびエッチング装置
US20220189781A1 (en) * 2020-12-11 2022-06-16 Tokyo Electron Limited Non-Atomic Layer Deposition (ALD) Method of Forming Sidewall Passivation Layer During High Aspect Ratio Carbon Layer Etch

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