TW202128958A - 蝕刻液,及半導體元件之製造方法 - Google Patents
蝕刻液,及半導體元件之製造方法 Download PDFInfo
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- TW202128958A TW202128958A TW109133836A TW109133836A TW202128958A TW 202128958 A TW202128958 A TW 202128958A TW 109133836 A TW109133836 A TW 109133836A TW 109133836 A TW109133836 A TW 109133836A TW 202128958 A TW202128958 A TW 202128958A
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- Prior art keywords
- etching solution
- acid
- etching
- sige
- compound
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- 238000005530 etching Methods 0.000 title claims abstract description 175
- 238000000034 method Methods 0.000 title claims description 22
- 239000004065 semiconductor Substances 0.000 title claims description 21
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- -1 hexafluorosilicic acid Chemical compound 0.000 claims abstract description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 14
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- 238000004519 manufacturing process Methods 0.000 claims description 16
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- 239000003495 polar organic solvent Substances 0.000 claims description 13
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- 238000005259 measurement Methods 0.000 claims description 5
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- AENSXLNDMRQIEX-UHFFFAOYSA-L oxido sulfate;tetrabutylazanium Chemical compound [O-]OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC AENSXLNDMRQIEX-UHFFFAOYSA-L 0.000 description 1
- MYKLQMNSFPAPLZ-UHFFFAOYSA-N p-xyloquinone Natural products CC1=CC(=O)C(C)=CC1=O MYKLQMNSFPAPLZ-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 235000008729 phenylalanine Nutrition 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
- TWWBIMNLBUYJKB-UHFFFAOYSA-N phosphanyl acetate Chemical compound CC(=O)OP TWWBIMNLBUYJKB-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- YPPQYORGOMWNMX-UHFFFAOYSA-L sodium phosphonate pentahydrate Chemical compound [Na+].[Na+].[O-]P([O-])=O YPPQYORGOMWNMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 229940063675 spermine Drugs 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- YNJQKNVVBBIPBA-UHFFFAOYSA-M tetrabutylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC YNJQKNVVBBIPBA-UHFFFAOYSA-M 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 description 1
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 description 1
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 description 1
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—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
- 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
- H01L21/02164—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 oxide, e.g. SiO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/302—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
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Abstract
一種蝕刻液,其係用以對Si、Ge及該等之氧化物選擇性蝕刻處理以通式Si1-x
Gex
表示之化合物(但,x超過0且未達1)之蝕刻液,且包含氟化物及氧化劑,前述氟化物包含六氟化矽酸,且藉以下條件測定之蝕刻速率A為10Å/min以上。
(A測定條件)
將於表面具有Si0.75
Ge0.25
層之覆層基板於25℃浸漬於蝕刻液,測定蝕刻速率。
Description
本發明有關蝕刻液及半導體元件之製造方法。
本申請案基於2019年10月4日向日本提出申請之特願2019-183804號及2020年9月16日向日本提出申請之特願2020-155651號主張優先權,其內容援用於本文。
過去以來,積體電路內之構成縮放能使半導體晶片上之機能單元高密度化。例如電晶體尺寸之縮小使得可於晶片上放入更多記憶體元件,而製造容量增加之製品。
用於積體電路裝置之場效電晶體(FET)之製造中,作為矽以外之半導體結晶材料,係使用Ge。Ge具有較高之電荷載子(電洞)移動度、帶隙偏移、不同晶格常數及與矽成為合金,生成SiGe之半導體二元合金之能力等,根據情況而異,具有與矽相比更有利之特徵。
已提案各種對Ge材料(尤其是以通式Si1-x
Gex
表示之化合物,但x超過0且未達1。以下有時簡稱為「SiGe化合物」)之選擇性高的蝕刻液。
例如專利文獻1中記載含有至少一種二醇化合物、至少一種氟化物種及至少一種氧化種之蝕刻組成物。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特表2018-519674號公報
[發明欲解決之課題]
然而,使用如專利文獻1中記載之以往蝕刻液之情況,不僅蝕刻SiGe化合物,亦會蝕刻Si或SiO2
等,難以相對於Si或SiO2
等而選擇性蝕刻SiGe化合物。
本發明係鑑於上述情況而完成者,其課題在於提供可對Si、Ge及該等之氧化物選擇性蝕刻處理以通式Si1-x
Gex
表示之化合物之蝕刻液、及使用該蝕刻液之半導體之製造方法。
[用以解決課題之手段]
為了解決上述課題,本發明採用以下構成。
本發明之第1態樣係一種蝕刻液,其係用以對Si、Ge及該等之氧化物選擇性蝕刻處理以通式Si1-x
Gex
表示之化合物(但,x超過0且未達1)之蝕刻液,且包含氟化物及氧化劑,前述氟化物包含六氟化矽酸,藉以下條件測定之蝕刻速率A為10Å/min以上。
(A測定條件)
將表面具有Si0.75
Ge0.25
層之覆層基板於25℃浸漬於蝕刻液,測定蝕刻速率。
本發明之第2態樣係一種半導體元件之製造方法,其包含使用前述蝕刻液,蝕刻處理含有以通式Si1-x
Gex
表示之化合物的被處理體之步驟。
[發明效果]
依據本發明之蝕刻液,可對Si、Ge及該等之氧化物選擇性蝕刻處理以通式Si1-x
Gex
表示之化合物。
又,依據本發明之半導體之製造方法,可製造對Si、Ge及該等之氧化物,以通式Si1-x
Gex
表示之化合物經選擇性蝕刻處理之半導體。
(蝕刻液)
本發明之第1態樣之蝕刻液包含氟化物及氧化劑,前述氟化物包含六氟化矽酸。本態樣之蝕刻液係用以對Si、Ge及該等之氧化物選擇性蝕刻處理以通式Si1-x
Gex
表示之化合物(但,x超過0且未達1)(以下有時簡稱為「SiGe化合物」)者。
本實施形態之蝕刻液藉以下條件測定之蝕刻速率A為10Å/min以上,較佳為15Å/min以上,更佳為20Å/min以上,又更佳為50Å/min以上,特佳為80Å/min以上。
(A測定條件)
將表面具有Si0.75
Ge0.25
層之覆層基板於25℃浸漬於蝕刻液,測定蝕刻速率。
本實施形態之蝕刻液藉由使前述蝕刻速率A為10Å/min以上,而成為對於SiGe化合物之選擇性良好。又,本實施形態之蝕刻液若前述蝕刻速率A為上述較佳範圍之下限值以上,則更提高對於SiGe化合物之選擇性。
本實施形態之蝕刻液若將藉以下條件測定之蝕刻速率設為蝕刻速率B時,較佳A/B為10以上,更佳A/B為15以上,又更佳A/B為20以上,又更佳A/B為30以上,又更佳A/B為70以上,特佳A/B為90以上。
(B測定條件)
將表面具有SiO2
層之覆層基板於25℃浸漬於蝕刻液,測定蝕刻速率。
本實施形態之蝕刻液藉由將A/B設為上述較佳範圍之下限值以上,可更提高相對於SiO2
之SiGe化合物的蝕刻選擇性。
<氟化物>
本實施形態之蝕刻液包含六氟化矽酸作為氟化物。
作為六氟化矽酸以外之氟化物並未特別限定,可舉例為六氟鈦酸、六氟矽酸、六氟鋯酸、四氟硼酸、三氟甲烷磺酸四丁基銨、四氟硼酸四丁基銨等之四氟硼酸四烷基銨(NR1
R2
R3
R4
BF4
)、六氟磷酸四烷基銨(NR1
R2
R3
R4
PF6
)、氟化四甲基銨等之氟化四烷基銨(NR1
R2
R3
R4
F) (其無水物或水合物)、重氟化銨、氟化銨(式中,R1
、R2
、R3
、R4
互為相同,亦可互為不同,且選自氫、直鏈或分支鏈之C1
-C6
烷基(例如甲基、乙基、丙基、丁基、戊基、己基)、C1
-C6
烷氧基(例如羥基乙基、羥基丙基)或取代或非取代芳基(例如苄基)所成之群)等。
本實施形態之蝕刻液中,較佳僅包含六氟化矽酸作為氟化物。
本實施形態之蝕刻液中,氟化物可單獨使用1種,亦可併用2種以上。
本實施形態之蝕刻液中之氟化物含量並未特別限定,但例示例如相對於蝕刻液總質量,為0.02~5質量%,較佳為0.025~3.00質量%,更佳為0.03~2.50質量%,又更佳為0.04~2.00質量%。氟化物含量若為前述範圍內,則更容易提高對於SiGe化合物之蝕刻速率。
又本實施形態之蝕刻液中之氟離子濃度並未特別限定,但例示為例如0.005~2.50mol/L,較佳為0.007~ 1.50mol/L,更佳為0.008~1.25mol/L,又更佳為0.010~ 1.00mol/L。氟離子濃度若在上述範圍內,則更容易提高對於SiGe化合物之蝕刻速率。
<氧化劑>
作為氧化劑舉例為例如過氧化氫、FeCl3
、FeF3
、Fe(NO3
)3
、Sr(NO3
)2
、CoF3
、MnF3
、過硫酸氫鉀(Oxone) (2KHSO5
・KHSO4
・K2
SO4
)、氫碘酸、氧化釩(V)、氧化釩(IV、V)、釩酸銨、過氧硫酸銨、亞氯酸銨、氯酸銨、碘酸銨、硝酸銨、過硼酸銨、過氯酸銨、過碘酸銨、過硫酸銨、次氯酸銨、次溴酸銨、鎢酸銨、過硫酸鈉、次氯酸鈉、過硼酸鈉、次溴酸鈉、碘酸鈉、過錳酸鉀、過硫酸鉀、硝酸、過硫酸鉀、次氯酸鉀、亞氯酸四甲基銨、氯酸四甲基銨、碘酸四甲基銨、過硼酸四甲基銨、過氯酸四甲基銨、過碘酸四甲基銨、過硫酸四甲基銨、過氧硫酸四丁基銨、過氧硫酸、硝酸鐵、過氧化脲、過乙酸、原過碘酸(H5
IO6
)、偏過碘酸(HIO4
)、甲基-1,4-苯醌(MBQ)、1,4-苯醌(BQ)、1,2-苯醌、2,6-二氯-1,4-苯醌(DCBQ)、甲苯醌、2,6-二甲基-1,4-苯醌(DMBQ)、四氯對苯醌(chloranil)、四氧嘧啶(alloxan)、N-甲基嗎啉N-氧化物、三甲基胺N-氧化物等。
其中,作為氧化劑較佳為硝酸或原過碘酸,更佳為硝酸。
本實施形態之蝕刻液中,氧化劑可單獨使用1種,亦可併用2種以上。
本實施形態之蝕刻液中之氧化劑含量可例示例如相對於蝕刻液總質量,為5~50質量%,較佳為5.5~45質量%,更佳為6~40質量%,又更佳為7~35質量%。
氧化劑含量若為上述範圍內,則SiGe化合物容易氧化,更容易提高對於SiGe化合物之蝕刻速率。
<其他成分>
本實施形態之蝕刻液在不損及本發明效果之範圍,除上述成分以外,亦可含有其他成分。作為其他成分舉例為例如溶劑、pH調整劑、鈍化劑、界面活性劑等。
・溶劑
本實施形態之蝕刻液較佳於溶劑中混合氫氟酸、氧化劑及其他任意成分而調製。
作為溶劑並未特別限定,舉例為水、極性有機溶劑、磷酸及/或其衍生物等。
・水
本實施形態之蝕刻液包含水作為溶劑之情況,水亦可含有不可避免混入之微量成分。本實施形態之蝕刻液所用之水較佳為蒸餾水、去離子水及超純水等之實施淨化處理之水,更佳使用半導體製造中一般使用之超純水。
本實施形態之蝕刻液包含水之情況,水之含量,例示為例如相對於蝕刻液總質量為3~50質量%,較佳為3.5~45質量%,更佳為4~40質量%,又更佳為4.5~40質量%。
・極性有機溶劑
本實施形態之蝕刻液,在不損及本發明效果之範圍內,亦可含有極性有機溶劑。作為極性有機溶劑舉例為有機羧酸系溶劑(例如乙酸、甲酸等)、醇系溶劑(例如甲醇、乙醇、乙二醇、丙二醇、甘油、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、二乙二醇、二丙二醇、糠醇及2-甲基-2,4-戊二醇等)、二甲基亞碸、醚系溶劑(例如乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、丙二醇二甲醚)等。
其中,作為極性有機溶劑較佳為有機羧酸系溶劑,更佳為乙酸。
本實施形態之蝕刻液中,極性有機溶劑可單獨使用1種,亦可併用2種以上。
本實施形態之蝕刻液包含極性有機溶劑之情況,極性有機溶劑之含量例示為例如相對於蝕刻液總質量,為20~90質量%,較佳為25~85質量%,更佳為30~80質量%,又更佳為35~75質量%。
・磷酸及其衍生物
本實施形態之蝕刻液,在不損及本發明效果之範圍內,亦可含有磷酸及/或其衍生物作為溶劑。作為磷酸及/或其衍生物舉例為下述通式(1)表示之化合物。
前述式(1)中,作為R中之碳數1~20之烷基舉例為甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、異十三烷基、十四烷基、十五烷基、十六烷基、異十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、上述烷基之各異構基等。
其中,作為R較佳為氫原子或碳數1~10之烷基,更佳為氫原子。
本實施形態之蝕刻液中,作為溶劑之磷酸及/或其衍生物可單獨使用1種,亦可併用2種以上。
本實施形態之蝕刻液中包含磷酸及/或其衍生物作為溶劑之情況,磷酸及/或其衍生物之含量例示為例如相對於蝕刻液總質量,為1~50質量%,較佳為2~45質量%,更佳為3~40質量%,又更佳為5~35質量%。
本實施形態之蝕刻液中,作為溶劑可單獨使用1種,亦可併用2種以上。
本實施形態之蝕刻液中,併用2種以上作為溶劑之情況,較佳為水與極性有機溶劑之組合或水與磷酸及/或其衍生物之組合,更佳為水與有機羧酸系溶劑之組合或水與磷酸及/或其衍生物之組合,更佳為水與乙酸之組合或水與磷酸之組合。
本實施形態之蝕刻液含有水與極性有機溶劑之組合作為溶劑之情況,水與極性有機溶劑之質量比較佳為1/15~1/1,更佳為1/12~ 9/10,又更佳為1/10~8/10。
本實施形態之蝕刻液含有水與磷酸及/或其衍生物之組合作為溶劑之情況,水與極性有機溶劑之質量比較佳為1/1~10/1,更佳為1.1/1~9/1,又更佳為1.2/1~ 8/1。
本實施形態之蝕刻液包含溶劑之情況,溶劑含量例示為例如相對於蝕刻液總質量,為23~95質量%,較佳為23.5~94.5質量%,更佳為24~94質量%。又更佳為24.5~93.5質量%。
・pH調整劑
本實施形態之蝕刻液為了更提高對於SiGe化和物之蝕刻速率,亦可包含pH調整劑。
作為pH調整劑較佳為選自酸及其鹽所成之群之至少1種。具體舉例為甲烷磺酸、三氟甲烷磺酸、草酸二水合物、檸檬酸、酒石酸、吡啶甲酸、琥珀酸、乙酸、乳酸、磺基琥珀酸、苯甲酸、丙酸、甲酸、丙酮酸、馬來酸、丙二酸、富馬酸、蘋果酸、抗壞血酸、扁桃酸、庚酸、丁酸、戊酸、戊二酸、苯二甲酸、次磷酸、水楊酸、5-磺基水楊酸、鹽酸、乙烷磺酸、丁烷磺酸、對-甲苯磺酸、二氯乙酸、二氟乙酸、單氯乙酸、單氟乙酸、三氟乙酸、三氟乙酸、氫溴酸(62重量%)、硫酸、乙酸銨、乙酸鈉、乙酸鉀、乙酸四甲基銨及其他乙酸四烷基銨、乙酸鏻、丁酸銨、三氟乙酸銨、碳酸銨、氯化銨、硫酸銨、磷酸、磷酸氫二銨、磷酸二氫銨、磷酸氫雙(四甲基銨)、磷酸氫二鈉、磷酸二氫鈉、磷酸氫二鉀、磷酸二氫鉀、磷酸氫二-四烷基銨、磷酸二氫二-四烷基銨、磷酸氫二鏻、磷酸二氫鏻、膦酸銨、膦酸四烷基銨、膦酸鈉、膦酸鉀、膦酸鏻、羥基亞乙基二膦酸該等之鹽等。
該等中,作為酸的pH調整劑較佳為甲烷磺酸或草酸。
又,本實施形態之蝕刻液亦可包含鹼性化合物作為pH調整劑。作為此等鹼性化合物可使用有機鹼性化合物及無機鹼性化合物,作為有機鹼化合物,作為較佳例舉例為以有機四級銨氫氧化物為代表之四級銨鹽、三甲基胺及三乙基胺等之烷基胺及其衍生物之鹽。
且,無機鹼性化合物舉例為包含鹼金屬或鹼土類金屬之無機化合物及其鹽。舉例為例如氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銣及氫氧化銫等。
本實施形態之蝕刻液中,pH調整劑可單獨使用1種,亦可併用2種以上。
本實施形態之蝕刻液包含pH調整劑之情況,pH調整劑含量例示為例如相對於蝕刻液總質量,為0.01~10質量%,較佳為0.02~4.5質量%,更佳為0.03~4質量%,又更佳為0.05~3質量%。pH調整劑含量若為上述範圍內,則更容易提高對SiGe化合物之蝕刻速率。
・鈍化劑
本實施形態之蝕刻液亦可包含鍺所用之鈍化劑。
作為鈍化劑,舉例為抗壞血酸、L(+)-抗壞血酸、異抗壞血酸、抗壞血酸衍生物、硼酸、二硼酸銨、硼酸鹽(例如五硼酸銨、四硼酸鈉及二硼酸銨)、丙胺酸、精胺酸、天門冬醯胺、天門冬胺酸、半胱胺酸、麩胺酸、麩醯胺酸、組胺酸、異白胺酸、白胺酸、離胺酸、甲硫胺酸、苯基丙胺酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸、溴化鈉、溴化鉀、溴化銣、溴化鎂、溴化鈣、具有式NR1
R2
R3
R4
Br(式中,R1
、R2
、R3
及R4
可彼此相同或可彼此不同,且選自氫及分支鏈或直鏈之C1
-C6
烷基(例如甲基、乙基、丙基、丁基、戊基、己基)所成之群)之溴化銨等。
本實施形態之蝕刻液中,鈍化劑可單獨使用1種,亦可併用2種以上。
本實施形態之蝕刻液包含鈍化劑之情況,例如相對於蝕刻液總質量,較佳為0.01~5質量%,更佳為0.1~1質量%。
・界面活性劑
本實施形態之蝕刻液為了調整蝕刻液對被處理體之濡濕性之目的等,亦可包含界面活性劑。作為界面活性劑可使用非離子界面活性劑、陰離子界面活性劑、陽離子界面活性劑或兩性界面活性劑,亦可併用該等。
作為非離子界面活性劑舉例為例如聚環氧烷烷基苯基醚系界面活性劑、聚環氧烷烷基醚系界面活性劑、由聚環氧乙烷與聚環氧丙烷所成之嵌段聚合物系界面活性劑、聚氧伸烷基二苯乙烯化苯基醚系界面活性劑、聚伸烷基三苄基苯基醚系界面活性劑、乙炔聚環氧烷系界面活性劑等。
作為陰離子界面活性劑舉例為例如烷基磺酸、烷基苯磺酸、烷基萘磺酸、烷基二苯基醚磺酸、脂肪酸醯胺磺酸、聚氧伸乙基烷基醚羧酸、聚氧伸乙基烷基醚乙酸、聚氧伸乙基烷基醚丙酸、烷基磺酸、脂肪酸之鹽等。作為「鹽」,舉例為銨鹽、鈉鹽、鉀鹽、四甲基銨鹽等。
作為陽離子界面活性劑舉例為例如四級銨鹽系界面活性劑或烷基吡啶鎓系界面活性劑等。
作為兩性界面活性劑舉例為例如甜菜鹼型界面活性劑、胺基酸型界面活性劑、咪唑啉型界面活性劑、胺氧化戊型界面活性劑等。
該等界面活性劑一般可由商業獲得。界面活性劑可單獨使用1種。亦可併用2種以上。
<被處理體>
本實施形態之蝕刻液係用以蝕刻SiGe化合物者,係以包含SiGe化合物之被處理體為蝕刻處理對象。被處理體只要包含SiGe化合物者,則未特別限定,但舉例為具有含SiGe化合物層(含SiGe化合物膜)之基板等。前述基板並未特別限定,舉例為半導體晶圓、光罩用玻璃基板、液晶顯示用玻璃基板、電漿顯示用玻璃基板、FED(場發射顯示器(Field Emission Display))用基板、光碟用基板、磁碟用基板、光磁碟用基板等之各種基板。作為前述基板較佳為用以製作半導體裝置所使用之基板。前述基板除了含SiGe化合物層及基板之基材以外,亦可適當具有各種層或構造,例如金屬配線、閘極構造、源極構造、汲極構造、絕緣層、強磁性層及非磁性層等。又,基板之裝置面的最上層並無必要為含SiGe化合物層,例如亦可多層構造之中間層為含SiGe化合物層。
基板之大小、厚度、形狀、層構造等並未特別限定,可根據目的適當選擇。
前述含SiGe化合物層較佳為含有SiGe化合物之層,更佳為SiGe化合物膜。基板上之含SiGe化合物層厚度並未特別限定,可根據目的適當選擇。作為含SiGe化合物層之厚度,舉例為例如1~500nm或1~300nm之範圍。
前述被處理體除了SiGe化合物以外,亦可包含選自由Si、Ge及該等之氧化物所成之群之至少1種,較佳包含SiO2
。
本實施形態之蝕刻液亦可使用於用以進行基板之含SiGe化合物層之微細加工,亦可使用於用以去除附著於基板之含SiGe化合物附著物,亦可用於用以自表面具有含SiGe化合物層之被處理體去除顆粒等之雜質。
依據以上說明之本實施形態之蝕刻液,由於包含六氟化矽酸作為氟化物,故可對Si、Ge及該等之氧化物選擇性蝕刻處理以通式Si1-x
Gex
表示之化合物(SiGe化合物)。其理由尚未確定,但推測如下。本實施形態之蝕刻液若與包含SiGe化合物之被處理體接觸,則藉由氧化劑使SiGe化合物氧化。SiGe化合物之氧化物藉由六氟化矽酸中之氟化物離子(F-
)而被蝕刻。另一方面,六氟化矽酸中之矽(Si)發揮保護被處理體中之Si或SiO2
等免於被氟化物離子(F-
)蝕刻之機能。因此,本實施形態之蝕刻液,與以往蝕刻液所用之氫氟酸(HF)或氟化銨(NH4
F)等之氟化物相比,推測相對Si、Ge及該等之氧化物,SiGe化合物之蝕刻選擇性提高。
(半導體元件之製造方法)
本發明之第2態樣之半導體元件之製造方法,其特徵係包含使用上述第1態樣之蝕刻液,蝕刻處理包含SiGe化合物的被處理體之步驟。
作為包含SiGe化合物的被處理體,舉例為與上述「(蝕刻液)」中之「<被處理體>」中說明者相同,較佳例示為具有含SiGe化合物層之基板。於基板上形成含SiGe化合物層之方法並未特別限定,可使用習知方法。作為該方法舉例為例如濺鍍法、化學氣相沉積(CVD:Chemical Vapor Deposition)法、分子線磊晶(MBE:Molecular Beam Epitaxy)法及原子層沉積法(ALD:Atomic layer deposition)等。於基板上形成含SiGe化合物層之際所用之含SiGe化合物層之原料亦未特別限定,可對應於成膜方法適當選擇。
前述被處理體除了SiGe化合物以外,亦可包含選自由Si、Ge及該等之氧化物所成之群之至少1種,較佳包含SiO2
。
<蝕刻處理被處理體之步驟>
本步驟係使用上述第1態樣之蝕刻液蝕刻處理包含SiGe化合物之被處理體之步驟,包含使前述蝕刻液與前述被處理體接觸之操作。蝕刻處理方法並未特別限定,可使用習知蝕刻方法。作為該方法例示有例如噴霧法、浸漬法、覆液法等,但不限定於該等。
噴霧法係例如使被處理體於特定方向搬送並旋轉,於其空間噴射上述第1態樣之蝕刻液,使前述蝕刻液與被處理體接觸。根據需要,亦可使用旋轉塗佈器,邊使基板旋轉邊噴霧前述蝕刻液。
浸漬法係將被處理體浸漬於上述第1態樣之蝕刻液,使前述蝕刻液與被處理體接觸。
覆液法係於被處理體上覆液上述第1態樣之蝕刻液,使被處理體與前述蝕刻液接觸。
該等蝕刻處理方法可對應於被處理體之構造或材料等適當選擇。噴霧法或覆液法之情況,前述蝕刻液對被處理體之供給量,只要被處理體中之被處理面以前述蝕刻液充分濡濕之量即可。
蝕刻處理之目的並未特別限定,可為被處理體之包含SiGe化合物之被處理面(例如基板上之含SiGe化合物層)之微細加工,亦可為附著於被處理體(例如具有含SiGe化合物層之基板)之含SiGe化合物附著物之去除,亦可為被處理體之包含SiGe化合物之被處理面(例如基板上之含SiGe化合物層)之洗淨。
蝕刻處理之目的為處理體之包含SiGe化合物之被處理面之微細加工之情況,通常不應被蝕刻之部位藉由蝕刻遮罩被覆後,使被處理體與蝕刻液接觸。
蝕刻處理之目的為附著於被處理體之含SiGe化合物附著物之去除的情況,藉由使上述第1態樣之蝕刻液與被處理體接觸,而將含SiGe化合物附著物溶解,可自被處理體去除SiGe化合物附著物。
蝕刻處理之目的為處理體之包含SiGe化合物之被處理面之洗淨的情況,藉由使上述第1態樣之蝕刻液與被處理體接觸,而將前述被處理面迅速溶解,使附著於被處理體表面之顆粒等之雜質於短時間自被處理體表面去除。
進行蝕刻處理之溫度並未特別限定,只要SiGe化合物於前述蝕刻液中可溶解之溫度即可。作為蝕刻處理之溫度舉例為例如15~60℃。噴霧法、浸漬法及覆液法之任一情況,均藉由提高蝕刻液之溫度而蝕刻速率上升,但亦考慮將蝕刻液之組成變化抑制為較小或作業性、安全性、成本等,而適當選擇處理溫度。
進行蝕刻處理之時間只要根據蝕刻處理之目的、藉由蝕刻去除之SiGe化合物之量(例如含SiGe化合物層之厚度、SiGe化合物附著物之量等)及蝕刻處理條件而適當選擇即可。
<其他步驟>
本實施形態之半導體元件之製造方法,除了上述蝕刻處理步驟以外,亦可包含其他步驟。其他步驟並未特別限定,舉例為製造半導體元件之際進行之習知步驟。作為該步驟,舉例為例如金屬配線、閘極構造、源極構造、汲極構造、絕緣層、強磁性層及非磁性層等之各構造形成步驟(層形成、上述蝕刻處理以外之蝕刻、化學機械研磨、變成等)、阻劑膜形成步驟、曝光步驟、顯像步驟、熱處理步驟、洗淨步驟、檢查步驟等,但不限定於該等。該等其他步驟根據需要,可於上述蝕刻處理步驟之前或之後適當進行。
依據以上說明之本實施形態之半導體元件之製造方法,使用包含六氟化矽酸作為氟化物之上述第1態樣之蝕刻液,進行被處理體之蝕刻處理。該蝕刻液可對Si、Ge及該等之氧化物選擇性蝕刻處理以通式Si1-x
Gex
表示之化合物(SiGe化合物)。因此,依據本實施形態之半導體元件之製造方法,可獲得Si、Ge及該等之氧化物實質上不受到影響,而SiGe化合物經選擇性蝕刻之半導體元件。
[實施例]
以下藉由實施例進一步詳細說明本發明,但本發明不受該等例之限制。
<蝕刻液之調製(1)>
(實施例1~9、比較例1~2)
混合表1所示之各成分,調製各例之蝕刻液。
表1中,各簡寫分別具有以下之意義。[ ]內之數值為調配量(質量%)。
H2
SiF6
:六氟化矽酸
HF:氫氟酸
NH4
F:氟化銨
HNO3
:硝酸
AcOH:乙酸
<被處理體之蝕刻處理(1)>
將表面具有Si0.75
Ge0.25
層之覆層基板於25℃浸漬於蝕刻液,測定蝕刻速率。結果示於表2。
<被處理體之蝕刻處理(2)>
將SOI基板於25℃浸漬於蝕刻液,測定蝕刻速率。結果示於表2。
<被處理體之蝕刻處理(3)>
將表面具有SiO2
層之覆層基板於25℃浸漬於蝕刻液,測定蝕刻速率。結果示於表2。
由表2所示之結果,確認實施例1~9之蝕刻液與比較例1~2之蝕刻液相比,SiGe蝕刻選擇比更高。
<蝕刻液之調製(2)>
(實施例10~13、比較例3~4)
混合表3所示之各成分,調製各例之蝕刻液。
表3中,各簡寫分別具有以下之意義。[ ]內之數值為調配量(質量%)。
H2
SiF6
:六氟化矽酸
HF:氫氟酸
HNO3
:硝酸
H3
PO4
:磷酸
<被處理體之蝕刻處理(1)>
將表面具有Si0.75
Ge0.25
層之覆層基板於25℃浸漬於蝕刻液,測定蝕刻速率。結果示於表4。
<被處理體之蝕刻處理(2)>
將SOI基板於25℃浸漬於蝕刻液,測定蝕刻速率。結果示於表4。
<被處理體之蝕刻處理(3)>
將表面具有SiO2
層之覆層基板於25℃浸漬於蝕刻液,測定蝕刻速率。結果示於表4。
由表4所示之結果,確認實施例10~13之蝕刻液與比較例3~4之蝕刻液相比,SiGe蝕刻選擇比更高。
以上說明本發明之較佳實施例,但本發明不受該等實施例之限制。在不脫離本發明主旨之範圍內,可進行構成之附加、省略、取代及其他變更。本發明並非由前述說明而限定,僅由隨附之申請專利範圍限定。
Claims (7)
- 一種蝕刻液,其係用以對Si、Ge及該等之氧化物選擇性蝕刻處理以通式Si1-x Gex 表示之化合物(但,x超過0且未達1)之蝕刻液, 且包含氟化物及氧化劑, 前述氟化物包含六氟化矽酸, 藉以下條件測定之蝕刻速率A為10Å/min以上, (A測定條件) 將表面具有Si0.75 Ge0.25 層之覆層基板於25℃浸漬於蝕刻液,測定蝕刻速率。
- 如請求項1之蝕刻液,其中進而含有極性有機溶劑。
- 如請求項1之蝕刻液,其中進而含有磷酸及/或其衍生物。
- 如請求項1之蝕刻液,其中前述氧化劑為硝酸。
- 如請求項1至4中任一項之蝕刻液,其中將藉以下條件測定之蝕刻速率設為蝕刻速率B時,A/B為10以上, (B測定條件) 將表面具有SiO2 層之覆層基板於25℃浸漬於蝕刻液,測定蝕刻速率。
- 一種半導體元件之製造方法,其包含使用如請求項1至5中任一項之蝕刻液,蝕刻處理含有以通式Si1-x Gex 表示之化合物的被處理體之步驟。
- 如請求項6之半導體元件之製造方法,其中前述被處理體進而包含SiO2 。
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