JP2019091890A - ドライエッチング方法 - Google Patents
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- JP2019091890A JP2019091890A JP2018197338A JP2018197338A JP2019091890A JP 2019091890 A JP2019091890 A JP 2019091890A JP 2018197338 A JP2018197338 A JP 2018197338A JP 2018197338 A JP2018197338 A JP 2018197338A JP 2019091890 A JP2019091890 A JP 2019091890A
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- carboxylic acid
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000001312 dry etching Methods 0.000 title claims abstract description 30
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 74
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000005530 etching Methods 0.000 claims abstract description 55
- 239000007789 gas Substances 0.000 claims abstract description 48
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 24
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 8
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004065 semiconductor Substances 0.000 claims abstract description 6
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims abstract description 4
- IPFHQCGGKGZQFJ-UHFFFAOYSA-N 2,2,3,3,4-pentafluorobutanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)CF IPFHQCGGKGZQFJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- PMWGIVRHUIAIII-UHFFFAOYSA-N 2,2-difluoropropanoic acid Chemical compound CC(F)(F)C(O)=O PMWGIVRHUIAIII-UHFFFAOYSA-N 0.000 claims abstract description 3
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
- H01L21/31116—Etching inorganic layers by chemical means by dry-etching
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- C09K13/00—Etching, surface-brightening or pickling compositions
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
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- H01L21/02107—Forming insulating materials on a substrate
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- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
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- H01L21/02518—Deposited layers
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- H01L21/67011—Apparatus for manufacture or treatment
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
添加量の上限は各化合物の蒸気圧とプロセス圧力から自ずと決定される。即ち、プロセス圧力が含フッ素カルボン酸の蒸気圧より低い場合、含フッ素カルボン酸の添加量が多くなりHFの濃度が低減するため、HFが不足してSiNのエッチングレートが十分に取れなくなる。そのため、添加量は最大でも、HFと含フッ素カルボン酸の濃度比(HF/含フッ素カルボン酸)が1以上となることが好ましい。
即ち、混合ガス中の含フッ素カルボン酸の添加量は、フッ化水素と前記含フッ素カルボンの合計の量の0.01体積%以上50体積%以下であることが好ましく、0.1体積%以上30体積%以下であることがより好ましく、3体積%以上15体積%以下であることがさらに好ましい。
試料4として、p−Si膜を有するシリコンウエハA、SiO2膜を有するシリコンウエハB、SiN膜を有するシリコンウエハCを反応装置1のステージ3上に設置した。SiN膜とp−Si膜は、それぞれCVD法により作製した。また、SiO2膜はシリコンウエハの表面を熱酸化して作製した。ステージの温度は70℃であった。ここに、HFとCF3COOHの混合ガス(HFが99.9体積%で、CF3COOHが0.1体積%である)を、総流量1000sccmとして流通させた。チャンバー内圧力は10kPaとし、エッチングを行った。
添加ガスの種類と濃度を変更した以外は、実施例1と同様にエッチング及び評価を行った。
2 チャンバー
3 ステージ
4 試料
5 ガス導入口
6 ガス排出ライン
7 圧力計
Claims (10)
- 窒化ケイ素に、フッ化水素と含フッ素カルボン酸を含む混合ガスを100℃未満かつプラズマレスで接触させ、前記窒化ケイ素をエッチングすることを特徴とするドライエッチング方法。
- 前記含フッ素カルボン酸の量が、前記フッ化水素と前記含フッ素カルボンの合計の量の0.01体積%以上であることを特徴とする請求項1に記載のドライエッチング方法。
- 前記含フッ素カルボン酸が、モノフルオロ酢酸、ジフルオロ酢酸、トリフルオロ酢酸、ジフルオロプロピオン酸、ペンタフルオロプロピオン酸、及びペンタフルオロ酪酸からなる群から選ばれる少なくとも一種であることを特徴とする請求項1または2に記載のドライエッチング方法。
- 前記混合ガスが、前記窒化ケイ素だけでなく、酸化ケイ素及び多結晶シリコンにも接触し、
前記窒化ケイ素と前記酸化ケイ素のエッチング選択比(SiN/SiO2)と、前記窒化ケイ素と前記多結晶シリコンのエッチング選択比(SiN/Si)がいずれも100以上であることを特徴とする請求項1に記載のドライエッチング方法。 - 前記含フッ素カルボン酸が、トリフルオロ酢酸又はペンタフルオロプロピオン酸であり、
前記含フッ素カルボン酸の量が、前記フッ化水素と前記含フッ素カルボンの合計の量の0.1体積%以上30体積%以下である
ことを特徴とする請求項1に記載のドライエッチング方法。 - 酸化ケイ素膜、多結晶シリコン膜及び窒化ケイ素膜を有するシリコン基板に対して、請求項1〜5のいずれかに記載のドライエッチング方法を適用して、選択的に窒化ケイ素膜をエッチングする工程を含むことを特徴とする半導体デバイスの製造方法。
- フッ化水素と含フッ素カルボン酸を含むドライエッチングガス組成物。
- 実質的にフッ化水素と含フッ素カルボン酸のみからなる請求項7に記載のドライエッチングガス組成物。
- 前記含フッ素カルボン酸の量が、前記フッ化水素と前記含フッ素カルボンの合計の量の0.01体積%以上であることを特徴とする請求項7または8に記載のドライエッチングガス組成物。
- 窒化ケイ素膜を有するシリコン基板を載置するステージを有するチャンバーと、
前記ステージに載置された前記基板に対して、フッ化水素と含フッ素カルボン酸を含むドライエッチングガス組成物を供給するためのガス供給部と、
前記チャンバー内を減圧するための真空排気部と、
前記ステージを加熱するためのヒーターと、
を備える、前記基板から前記窒化ケイ素膜をエッチングするエッチング装置。
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WO2022176142A1 (ja) * | 2021-02-19 | 2022-08-25 | 株式会社日立ハイテク | エッチング方法およびエッチング装置 |
KR20240101508A (ko) | 2022-12-19 | 2024-07-02 | 주식회사 히타치하이테크 | 에칭 방법 |
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KR20240101508A (ko) | 2022-12-19 | 2024-07-02 | 주식회사 히타치하이테크 | 에칭 방법 |
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JP7177344B2 (ja) | 2022-11-24 |
US20200365411A1 (en) | 2020-11-19 |
US11289340B2 (en) | 2022-03-29 |
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