TW201710555A - 用於乾氣相化學蝕刻一結構之方法及設備 - Google Patents
用於乾氣相化學蝕刻一結構之方法及設備 Download PDFInfo
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- TW201710555A TW201710555A TW105123267A TW105123267A TW201710555A TW 201710555 A TW201710555 A TW 201710555A TW 105123267 A TW105123267 A TW 105123267A TW 105123267 A TW105123267 A TW 105123267A TW 201710555 A TW201710555 A TW 201710555A
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- 238000005530 etching Methods 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000000126 substance Substances 0.000 claims abstract description 35
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- -1 halogen fluoride Chemical class 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 38
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 22
- 239000012808 vapor phase Substances 0.000 claims description 21
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 18
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 18
- 238000003486 chemical etching Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 9
- OPBNKGCNCRNWLP-UHFFFAOYSA-L [Bi](F)F Chemical group [Bi](F)F OPBNKGCNCRNWLP-UHFFFAOYSA-L 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
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- 229910052732 germanium Inorganic materials 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910052581 Si3N4 Inorganic materials 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 abstract 1
- 229910052756 noble gas Inorganic materials 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract 1
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 11
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 9
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- 238000010926 purge Methods 0.000 description 8
- 229910052707 ruthenium Inorganic materials 0.000 description 8
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- 238000003860 storage Methods 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 6
- 230000002000 scavenging effect Effects 0.000 description 5
- BLIQUJLAJXRXSG-UHFFFAOYSA-N 1-benzyl-3-(trifluoromethyl)pyrrolidin-1-ium-3-carboxylate Chemical compound C1C(C(=O)O)(C(F)(F)F)CCN1CC1=CC=CC=C1 BLIQUJLAJXRXSG-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229940119177 germanium dioxide Drugs 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- OUJISMBVLMMJNR-UHFFFAOYSA-L dicesium;difluoride Chemical class [F-].[F-].[Cs+].[Cs+] OUJISMBVLMMJNR-UHFFFAOYSA-L 0.000 description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- SPPCMVNDPDQNRG-UHFFFAOYSA-L [F-].[F-].[Sb++] Chemical compound [F-].[F-].[Sb++] SPPCMVNDPDQNRG-UHFFFAOYSA-L 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- UZBMLWGAEQOROI-UHFFFAOYSA-L difluororuthenium Chemical compound F[Ru]F UZBMLWGAEQOROI-UHFFFAOYSA-L 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- YQFVVQITNLEBHI-UHFFFAOYSA-L [F-].[F-].[Hf+2] Chemical compound [F-].[F-].[Hf+2] YQFVVQITNLEBHI-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005112 continuous flow technique Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- GGJOARIBACGTDV-UHFFFAOYSA-N germanium difluoride Chemical compound F[Ge]F GGJOARIBACGTDV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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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
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- H01L21/3105—After-treatment
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- 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
- H01L21/02118—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 carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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Abstract
本發明係提供乾氣相化學蝕刻一結構之方法,包含下列步驟:於一蝕刻室定位該結構,該結構包含一第一材料及一第二材料,其中第一材料係選自於矽、鉬、鍺、矽鍺、及鎢,第二材料係二氧化矽或氮化矽,且第一材料之至少一表面係經曝露,以便可由氣相化學蝕刻劑接觸;以及以惰性氣體氟化物或鹵素氟化物氣相化學蝕刻劑蝕刻第一材料;本方法進一步包含將蝕刻室曝露於水蒸氣之步驟,以使蝕刻第一材料之步驟於水蒸氣存在下進行。
Description
本發明係有關乾氣相化學蝕刻一結構之方法。本發明亦有關用於乾氣相化學蝕刻一結構之設備。
本發明解決了半導體製造領域中常遇到的及長期存在之問題。該問題涉及包含矽與二氧化矽或氮化矽兩者之結構,其中有需要蝕刻該結構之矽部分。該結構之二氧化矽及/或氮化矽部分可以遮罩(mask)或自身之永久性結構特徵存在。問題在於,用於蝕刻矽之過程亦攻擊二氧化矽及氮化矽。非常需要改進矽對二氧化矽與氮化矽之蝕刻選擇性,係因此選擇性之改進可減少二氧化矽或氮化矽之厚度,其為欲成功進行矽蝕刻過程所需。其反而減少成本,同時提供設計靈活性。選擇性於此定義為,經蝕刻之靶材(如矽)之量與經蝕刻之二氧化矽及/或氮化矽之量的比率。欲改進蝕刻選擇性,有各種提案提出,其係藉由在蝕刻過程之各點導入各氣體。US6290864提出使用蝕刻劑與非蝕刻劑如氦之摻和物。GB2473851揭示使用氫,且US7041224
揭示使用氫及/或氧,於兩情況下,皆用作結合蝕刻劑之摻和物之一部分。WO2011/006895提出在蝕刻過程之各階段中使用氧及/或氧化氣體,如一氧化二氮、臭氧、或二氧化氮。彼等氧化氣體需要額外加熱以發揮效用。
本發明,於其實施例之至少一些之中,提供乾氣相化學蝕刻一結構之方法,並具改進之選擇性。應理解的是,乾氣相化學蝕刻意指以氣相化學蝕刻劑蝕刻,其不需要存在電漿或另一高能之分離蝕刻劑方式,以進行蝕刻。亦應理解的是,術語「氣相」包括參照氣相物種或存在於氣相之經昇華物種。
根據本發明之第一態樣,係提供乾氣相化學蝕刻一結構之方法,其步驟包含:於蝕刻室定位該結構,該結構包含第一材料及第二材料,其中第一材料係選自於矽、鉬、鍺、矽鍺、及鎢,第二材料係二氧化矽或氮化矽,且第一材料之至少一表面係經曝露,以便可由氣相化學蝕刻劑接觸;以及以惰性氣體氟化物或鹵素氟化物氣相化學蝕刻劑蝕刻第一材料;本方法進一步包含將蝕刻室曝露於水蒸氣之步驟,以使蝕刻第一材料之步驟於水蒸氣存在下進行。
本領域之普遍知識認為,在以惰性氣體氟化物或鹵素氟化物蝕刻期間,若蝕刻室存在濕氣,蝕刻劑將導致
氟化氫形成,其反過來將蝕刻二氧化矽。US6939409提供此公認智識之實例。可以預期,這將導致矽對二氧化矽之劣質蝕刻選擇性。氮化矽亦受氟化氫影響,因此可預期,濕氣之存在亦將導致矽對二氧化矽之劣質蝕刻選擇性。因此,令人非常驚訝的是,本發明可產生極佳及改進之蝕刻選擇性。
將蝕刻室曝露於水蒸氣之步驟可包含將水蒸氣導入蝕刻室,且之後於蝕刻第一材料之步驟前自蝕刻室移除水蒸氣。
將水蒸氣導入蝕刻室、自蝕刻室移除水蒸氣、及蝕刻基板之步驟可循環重複。於彼等實施例中,在蝕刻第一材料之步驟後及後續將蝕刻室曝露於水蒸氣之步驟前,可自蝕刻室移除氣相化學蝕刻劑。以惰性氣體氟化物或鹵素氟化物氣相蝕刻劑蝕刻第一材料之初始步驟可於將水蒸氣導入蝕刻室、自蝕刻室移除水蒸氣、及蝕刻基板等步驟之循環重複前進行。
將蝕刻室曝露於水蒸氣之步驟可包含在將氣相化學蝕刻劑導入蝕刻室之同一時間將水蒸氣導入蝕刻室。氣相化學蝕刻劑及水蒸氣可連續流入蝕刻室。或者,氣相化學蝕刻劑及水蒸氣可於同一時間以一系列脈衝導入蝕刻室。
氣相化學蝕刻劑及水蒸氣可分別導入蝕刻室。這可經由氣相化學蝕刻劑及水蒸氣使用單獨氣體管線與進氣口而達成。或者,氣相化學蝕刻劑及水蒸氣於導入蝕刻
室前可充分混合。彼等方法學可作為將蝕刻室曝露於水蒸氣之連續流或脈衝式方法之一部分。
於單一蝕刻過程中,上述方法之組合可用於將蝕刻室曝露於水蒸氣。
於蝕刻室蝕刻第一材料之步驟期間,水蒸氣於蝕刻室之分壓可低於氣相化學蝕刻劑於蝕刻室之分壓。於蝕刻第一材料之步驟期間,水蒸氣於蝕刻室之分壓與氣相化學蝕刻劑於蝕刻室之分壓的比率可低於0.5:1。
化學蝕刻劑可為二氟化氙(XeF2)。或者,化學蝕刻劑可為XeF4、XeF6、KrF2、ClF3、BrF3、或IF5。
將蝕刻室曝露於水蒸氣之步驟可包含於壓力至少5托(667帕)下將水蒸氣導入蝕刻室。水蒸氣之壓力可為至少10托(1333帕)。水蒸氣可於壓力約12托(1600帕)下導入蝕刻室。
水蒸氣可於溫度低於30℃下導入蝕刻室。水蒸氣可為室溫或稍高於室溫(例如,高於室溫5℃或以下)。一般而言,毋須於高溫下使用水蒸氣。
將蝕刻室曝露於水蒸氣之時間可不超過20秒。
結構可以第一材料對第二材料之蝕刻選擇性至少2,500,較佳地至少4,000,更佳地至少10,000,且最佳地至少20,000,化學蝕刻。於彼等實施例中,第一材料可為矽。第二材料可為二氧化矽。
當第二材料為氮化矽時,結構可以第一材料對第二材料之蝕刻選擇性至少6000化學蝕刻。第一材料可為矽。
本領域之讀者應理解到,氮化矽樣本之精確組成物可依各因子而變,如沉積條件。氮化矽可以SixNy陳述,其中x與y係不固定,且典型而言分別接近3與4。
結構所存在之二氧化矽及氮化矽可藉由任何適用之技術產生,如CVD(化學蒸氣沉積)或物理沉積方法。可使用矽之熱氧化、低壓CVD(LPCVD)、或電漿化學CVD(PECVD)。二氧化矽及氮化矽可以薄膜形式存在,其可為薄層薄膜(thin films)。
第一及第二材料之所有結合物皆落入本發明之範疇。
本發明之第二態樣係提供結構及設備,用於乾氣相化學蝕刻本發明第一態樣方法之結構,其中,設備包含:一蝕刻室,其中結構係經定位;一第一源之惰性氣體氟化物或鹵素氟化物氣相化學蝕刻劑;一第二源,其含有一體積之水;以及一氣體輸送與移除系統,包含一控制器,其容許i)將蝕刻室曝露於第二源供應之水蒸氣,及ii)於水蒸氣存在下以第一源供應之氣相化學蝕刻劑蝕刻結構;且結構包含第一材料及第二材料,其中第一材料係選自於矽、鉬、鍺、矽鍺、及鎢,第二材料係二氧化矽或氮化矽,且第一材料之至少一表面係經曝露,以便可由氣相化學蝕刻劑接觸。
應理解的是,本發明第一態樣所述之任何特徵,亦於本發明第二態樣中描述,反之亦然。
儘管本發明說明如上,其可延伸至任何本發明中前述特徵之組合,或以下之說明、圖示、或申請專利範圍。
10‧‧‧控制器
12‧‧‧氣相蝕刻劑源
14‧‧‧閥
16‧‧‧膨脹室
18‧‧‧蝕刻室
20‧‧‧閥
22‧‧‧貯槽
24‧‧‧閥
26‧‧‧閥
28‧‧‧真空泵
30‧‧‧閥
50‧‧‧矽基板
52‧‧‧二氧化矽層
100‧‧‧控制閥
101‧‧‧質量流量控制器
102‧‧‧控制閥
103‧‧‧閥
120‧‧‧晶圓
122‧‧‧矽基板
124‧‧‧二氧化矽或氮化矽層
126‧‧‧聚矽層
128‧‧‧光阻圖案
140‧‧‧壓力控制閥
150‧‧‧壓力感測器
200‧‧‧控制閥
201‧‧‧質量流量控制器
202‧‧‧控制閥
300‧‧‧真空密閉貯槽
現將參照所附圖示,說明本發明設備及方法之實施例,其中:圖1係本發明第一設備之示意圖;圖2係受測晶圓於蝕刻前之剖面圖;圖3係受測晶圓於蝕刻後之剖面圖;圖4係本發明第二、連續流動設備之示意圖;以及圖5係蝕刻(a)前與(b)後於矽上熱生長二氧化矽之受測晶圓剖面圖。
圖1顯示用於氣相化學蝕刻一結構(未顯示)之設備,本設備包含氣相蝕刻劑源12。於本範例中,氣相蝕刻劑為二氟化氙,且化學蝕刻劑源12含有氣相二氟化氙,其係固體二氟化氙之昇華物,其亦存在於源12。可考量其他稀有氣體氟化物及鹵素氟化物。閥14可開啟與關閉,以容許中間室16(通常稱作膨脹室)填充二氟化氙至所需壓力。欲蝕刻之結構(未顯示)係裝入蝕刻室18。結構之裝載可以本領域充分理解之技術及設備進行。閥20可開啟與關閉,以便控制氣相化學蝕刻劑導入室18以蝕刻結構。設備進一步
包含貯槽22,其係部分以水填充。閥24可開啟,以容許水蒸氣進入蝕刻室18。預先抽空存在於貯槽22之任何空氣,以使貯槽22之氣體環境完全由水蒸氣組成。一具閥26之排氣管係連接至真空泵28。如此使得氣體自蝕刻室18泵出。設備包含具閥30之輔助排氣管,其使膨脹室16藉由真空泵28抽空。根據本發明,設備進一步包含控制器10,其控制設備之各元件操作,包括閥14、20、24、26、及30。為了簡單呈現,圖1未顯示控制器10與設備之各控制元件間之互連。控制器可為任何適用形式,如PC、PLC、或其他微處理器為主之裝置。
現將說明本發明設備之操作方法。貯槽22係處於室溫。於室溫下,水蒸氣於貯槽22中係位於液態水上方,其蒸氣壓約17托。閥24係開啟,以允許水蒸氣流入蝕刻室18。水係自存在於貯槽之液態水蒸發,以維持貯槽22之室溫壓力,且只要閥24開啟,水蒸氣於蝕刻室18之壓力增至接近水之蒸氣壓。設備可易於設計成該過程以足夠慢之方式進行(如在一段數秒鐘之時間內),其中閥24可由控制器10控制,以在蝕刻室18達到目標水蒸氣壓時,關閉水蒸氣供應至蝕刻室18。將顯見的是,此一主室18之目標蒸氣壓可對應於完全水蒸氣壓,或者可達到目標壓力低於完全水蒸氣壓。於水蒸氣導入室18期間,閥26連同閥20皆關閉。將蝕刻室18於所需時間及所需壓力下曝露於水蒸氣後,藉由開啟閥26將水蒸氣泵出主室18,直到蝕刻室18達到實際基礎壓力為止。水蒸氣於主室18之典型滯留時間係數秒,且
蝕刻室於移除水蒸氣後之典型實際基礎壓力約0.3托。自蝕刻室18移除水蒸氣即完成水蒸氣清除循環。
一蝕刻循環隨即形成。開啟閥14,以容許二氟化氙蒸氣填充膨脹室16。隨後關閉閥14。含有欲蝕刻結構之蝕刻室18係處於所需之基礎壓力(如0.3托),其係藉由真空泵28泵送通過閥26。隨後關閉閥26,開啟閥20,且二氟化氙氣體於一所需時間內自膨脹室16流入蝕刻室18。於此所需時間結束時,開啟閥26,以容許真空泵28將蝕刻室18抽真空。此過程可伴隨開啟閥20而進行,以使膨脹室16部分或完全抽空。於此情況下,膨脹室16可抽真空至特定壓力,其可低於0.8托。隨即關閉閥20,且開啟閥30,以完全抽空膨脹室16至所需基礎壓力。所需基礎壓力可約0.3托或以下。隨即關閉閥30。如此完成一蝕刻循環。可以循環方式重複蝕刻及水蒸氣循環,直到蝕刻室18之結構蝕刻一所需材料量。過程中進行之第一步驟可為蝕刻循環或水蒸氣清除循環。設備之示意圖如圖1所示。本領域讀者應理解到,化學蝕刻系統之各元件係本領域習知,如壓力感測器及其他組件,其存在於設備但未顯示於圖1。
進行許多實驗,其中含矽受測晶圓係經蝕刻。圖2顯示蝕刻前之受測晶圓,整體以120說明。晶圓120包含矽基板122,其具二氧化矽或氮化矽層124。更特別的是,1微米厚二氧化矽層係熱生長而成,且0.3微米厚化學計量SixNy層係藉由LPCVD沉積。1微米厚之LPCVD無摻雜聚矽層126係沉積於二氧化矽或氮化矽層124之上。1微米厚之光阻圖
案128係於聚矽層126之上形成。圖3代表以二氟化氙化學蝕刻後之受測晶圓120。圖2與圖3使用相同標號,以表示相同特徵。光阻128下方係蝕刻一定量之矽。此一定量經蝕刻之矽之程度係稱作基蝕(undercut)。測量基蝕,同時測量剩餘之二氧化矽或氮化矽層124厚度。經由彼等測量,可計算蝕刻選擇性。矽對二氧化矽或氮化矽之蝕刻選擇性係矽蝕刻基蝕距離與二氧化矽或氮化矽薄層厚度減少之比率。
實驗結果連同一些實驗參數係顯示於表1。於所有實驗中,所用蝕刻室係配備石英蓋(quartz lid)以最小化濕氣變化,且容許肉眼檢查蝕刻過程。矽晶圓係保留於蝕刻室之夾頭上。室及夾頭溫度設定為24℃。二氟化氙係存在於膨脹室,各蝕刻循環之壓力為6托,且各循環之間蝕刻室之抽出係低於0.3托。若進行清除,則蝕刻室於抽出至低於0.3托之前,清除循環包含將氣體保留於蝕刻室中5秒。各實驗包含二氧化矽層晶圓及氮化矽層晶圓之單獨測試。
於實驗#1,執行蝕刻,且蝕刻循環間無任何清除。此過程從而可描述成基本上包含將晶圓曝露於一系列二氟化氙脈衝。此為典型之蝕刻過程先前技術,且其導致氮化矽之選擇性370且二氧化矽之選擇性1378。
於各二氟化氙脈衝後,採取水蒸氣清除。於水蒸氣清除期間,蝕刻室之水蒸氣壓為12托,且其於抽出蝕刻室至低於0.3托前維持5秒。由於以水填充蝕刻室、維持水蒸氣壓、及抽出之過程,增加水蒸氣清除,係另外加上約17秒至該過程。相較於參考實驗,所得選擇性顯示急遽增加。由於二氧化矽,選擇性有約350%之增加,而由於氮化矽,選擇性增加約2000%。據指出,相較於參考實驗,矽之基蝕距離下降約25%。不希望受到任何特定理論或推測
之束縛,據信二氟化氙可與水反應,其減少可用於蝕刻矽之二氟化氙量。有許多應用,其最大化矽對氮化矽與二氧化矽之選擇性,為最關鍵之需求,且其中此需求比整體矽蝕刻率更重要。此外,可能改變室(chamber)之水蒸氣壓,以提供如所需之調整矽蝕刻率與選擇性之方式。舉例而言,可使用較低之水蒸氣壓,目的在於增加矽蝕刻率。另一可能性為使用不同蝕刻順序,其中水蒸氣清除係僅於使用數次蝕刻脈衝後進行。進一步之可能係使用連續流蝕刻過程,其中在氣體流動停止且蝕刻室抽空之前,二氟化氙(或其他蝕刻劑)於指定之蝕刻室壓力下流動一定時間。水蒸氣脈衝或流隨即可於指定時間與指定壓力下導入蝕刻室。此一以偶爾停止導入水蒸氣所進行的連續蝕刻過程可重複,直到完成蝕刻過程。
進行多個其他實驗以作為比較。在實驗#3,於蝕刻步驟前,加入17秒的延遲時間。此實驗之其他部分與參考實驗#1相同。17秒延遲時間對應於進行水蒸氣清除步驟之總時間。相較於參考實驗#1,選擇性未明顯改變,儘管經蝕刻矽之總量增加約10%。這可藉由在蝕刻週期之間冷卻晶圓而加以解釋,係因較低溫習知可增加二氟化氙蝕刻矽之蝕刻率。實驗#3顯示,於蝕刻週期之間簡單導入時間延遲(time lag),無法驅動改進之蝕刻選擇性。
實驗#4遵循實驗#2之相同程序,除了以氮氣而非水蒸氣進行清除以外。氮氣係經導入至壓力12托,其與實
驗#2之蝕刻室存在之水蒸氣壓相同。所得選擇性類似參考實驗#1,儘管矽蝕刻率似乎增加。事實上,一些證據顯示,蝕刻率比實驗#3取得的大。此將與氮氣環境一致,其於蝕刻週期之間提供進一步之晶圓冷卻,且預期能增加蝕刻率。實驗#4證實,改進之選擇性並非僅是蝕刻週期之間於壓力12托下清除氣體之結果。
實驗#5及6係以氧氣代替水蒸氣。彼等實驗之目的在於探討氧是否為選擇性增加之主要成因。以6與12托之氧壓測試是否相同數目之氧原子或相同數目之氧莫耳數可解釋改進之選擇性。然而,於兩情況下,相較於以水蒸氣清除所觀察到選擇性350%與2000%之改進,似乎僅相對適度增加不超過55%。矽蝕刻率似乎至少如同參考蝕刻一般快速。
實驗#7利用分子氫氣清除,觀察氫是否為選擇性改進之主要來源。於此情況下,於蝕刻週期間使用12托之氫。氮化矽之選擇性似乎變差,而二氧化矽則輕微改進(29%增加)。矽蝕刻率約略與參考蝕刻相同。
實驗證實,相較於二氧化矽及氮化矽,於蝕刻週期之間使用水蒸氣清除,可提供顯著改進矽之蝕刻選擇性。彼等改進似乎特別與使用水蒸氣相關聯。特別是,其益處無法以水清除步驟延遲蝕刻一額外時間、於特定壓力下本身使用清除氣體、或水之原子組分之單獨作用等解釋。
進一步之測試係以一連續流蝕刻系統進行,其容許水蒸氣伴隨蝕刻氣體流動。系統如圖4所示,且含有許多
如圖1所示之相同元件。圖1所用之參考標號與圖4的相同,以表示彼等共享之元件。將一晶圓(或樣本-未顯示)裝入蝕刻室(18),其亦稱作加工室(process chamber),且室18係泵送至適當低壓,如0.3托,其係藉開啟主真空閥26及壓力控制閥140。室18之壓力係由壓力感測器150監測,其係以壓力控制閥140設定。壓力控制閥140發送一過程蝕刻壓力設定,如1托。壓力控制閥可為習知之APC(自動化壓力控制器)類型。大約同一時間,二氟化氙與水蒸氣流藉由開啟來源閥14及二氟化氙控制閥100與102及水蒸氣控制閥200與202而啟動。MFCs(質量流量控制器)101與201係用於校正二氟化氙與水之流速。晶圓蒸氣係源自真空密閉貯槽300,其事先部分裝水,並排除空氣。於室溫下,水上方空間係以水蒸氣充填,其蒸氣壓約17托。
彼等流動於蝕刻過程期間維持不變,且室壓維持在壓力控制閥140設定之設定點。於過程結束時,關閉閥100與102,若使用水蒸氣,則亦關閉200與202。完全開啟壓力控制閥140以泵送室至低壓,如低於0.3托,且進行數次泵送/清除循環,其係藉由關閉主真空閥26、流入通氣103,其典型上為氮,直至壓力如30托、關閉閥103、及之後開啟閥26,且在移除晶圓之前重複此過程數次。
欲簡單表示,控制器10,如PC或PLC控制器,係如圖1之10的設定,但未顯示於圖4。典型上有額外的閥(未顯示)泵送或清除MFCs 101與201。此連續流過程可與脈衝系統整合。藉由增加容器300中之水溫,以增加水蒸氣流
速。或者,可使用水蒸發器。
以連續流操作方式運行另一類受測晶圓,作為二氧化矽選擇性之更靈敏測試。此類受測晶圓(XO)由矽基板50組成,其上熱生長1微米之二氧化矽層52(圖5a)。隨後,二氧化矽層以500-um之方孔陣列圖案化,其具2500-um間距,因此約略4%之晶圓區域係曝露於矽。於蝕刻前與後,二氧化矽薄膜皆位於晶圓表面上,因此可進行更精確之厚度測量,並與二氧化矽層位於蝕刻矽層下方之受測晶圓相比較(沿晶圓直徑將5個點的厚度測量值平均,以進一步增加精確度)。蝕刻過程使基板產生凹坑(pits)(圖5b),且蝕刻量可以光學方式由橫向蝕刻(或「基蝕」)確認。如同其他類型之受測晶圓,彼等受測晶圓使用同一機器設定及配方。
表2係建立以水與蝕刻氣體之益處所使用之條
件,其可見於運行號8,係作為210秒蝕刻週期之參考點。藉由添加9.6sccm之水至30sccm之參考二氟化氙氣流,發明人可觀察到矽/二氧化矽選擇性之極實質改進,804:1至>27,419:1。亦觀察到蝕刻率(基蝕值)之改進。
不希望受限於任何特定理論或推測,據信以微量之水結合並中和游離之氟基,視為負責蝕刻二氧化矽與氮化矽。
可有許多修改及變體。舉例而言,僅特定蝕刻步驟間可進行水蒸氣清除步驟。另一可能為,停止連續流蝕刻及進行水蒸氣清除之前,進行一段時間之連續流蝕刻。一水蒸氣脈衝或流可於一指定壓力及一指定時間內導入蝕刻室。其後,可恢復連續流蝕刻過程。視需求,可重複多次停止連續流蝕刻及進行水蒸氣清除。儘管本發明列舉使用二氟化氙之矽蝕刻,仍可使用其他蝕刻劑及蝕刻其他材料。舉例而言,利用本發明,可選擇性蝕刻之材料如鉬、鍺、矽鍺、及鎢。亦可使用其他蝕刻劑,如KrF2、XeF4、XeF6、ClF3、BrF3、及IF5。
10‧‧‧控制器
12‧‧‧氣相蝕刻劑源
14‧‧‧閥
16‧‧‧膨脹室
18‧‧‧蝕刻室
20‧‧‧閥
22‧‧‧貯槽
24‧‧‧閥
26‧‧‧閥
28‧‧‧真空泵
30‧‧‧閥
Claims (18)
- 一種乾氣相化學蝕刻一結構之方法,包含下列步驟:於一蝕刻室定位該結構,該結構包含一第一材料及一第二材料,其中該第一材料係選自於矽、鉬、鍺、矽鍺、及鎢,該第二材料係二氧化矽或氮化矽,且該第一材料之至少一表面係經曝露,以便可由氣相化學蝕刻劑接觸;以及以惰性氣體氟化物或鹵素氟化物氣相化學蝕刻劑蝕刻該第一材料;該方法更包含將該蝕刻室曝露於水蒸氣之步驟,以使該蝕刻第一材料之步驟於水蒸氣存在下進行。
- 如請求項1之方法,其中將該蝕刻室曝露於水蒸氣之步驟包含將水蒸氣導入該蝕刻室,且之後於該蝕刻第一材料之步驟前自該蝕刻室移除水蒸氣。
- 如請求項2之方法,其中將水蒸氣導入該蝕刻室、自該蝕刻室移除水蒸氣、及蝕刻基板之步驟係循環重複。
- 如請求項3之方法,其中以惰性氣體氟化物或鹵素氟化物氣相化學蝕刻劑蝕刻該第一材料之初始步驟係於將水蒸氣導入該蝕刻室、自該蝕刻室移除水蒸氣、及蝕刻該基板等步驟之循環重複前進行。
- 如請求項1之方法,其中該曝露蝕刻室於水蒸氣之步驟包含在將氣相化學蝕刻劑導入該蝕刻室之同一時間將水蒸氣導入該蝕刻室。
- 如請求項5之方法,其中該氣相化學蝕刻劑及該水蒸氣係連續流入該蝕刻室。
- 如請求項5之方法,其中該氣相化學蝕刻劑及該水蒸氣係於同一時間以一系列脈衝導入該蝕刻室。
- 如請求項5之方法,其中該氣相化學蝕刻劑及該水蒸氣係分別導入該蝕刻室。
- 如請求項5之方法,其中該氣相化學蝕刻劑及該水蒸氣係於其導入該蝕刻室前充分混合。
- 如請求項1之方法,其中該化學蝕刻劑係二氟化氙。
- 如請求項1之方法,其中該曝露蝕刻室於水蒸氣之步驟包含於壓力至少5托下將水蒸氣導入該蝕刻室。
- 如請求項11之方法,其中該水蒸氣係於壓力至少10托下導入該蝕刻室。
- 如請求項1之方法,其中於該蝕刻第一材料之步驟期間,該水蒸氣於蝕刻室之分壓係低於該氣相化學蝕刻劑於蝕刻室之分壓。
- 如請求項1之方法,其中該水蒸氣係於低於30℃之溫度下導入該蝕刻室。
- 如請求項1之方法,其中該水蒸氣導入該蝕刻室之時間不超過20秒。
- 如請求項1之方法,其中該結構係以該第一材料對該第二材料之蝕刻選擇性至少2,500,較佳地至少4,000,更佳地至少10,000,且最佳地至少20,000,來進行化學蝕刻。
- 如請求項16之方法,其中該第二材料係氮化矽,且該結構係以該第一材料對該第二材料之蝕刻選擇性至少6000來進行化學蝕刻。
- 一種結構及設備,係用於乾氣相化學蝕刻如請求項1方法之結構,其中該設備包含:一蝕刻室,其中該結構係經定位;一第一源之惰性氣體氟化物或鹵素氟化物氣相化學蝕刻劑;一第二源,其含有一體積之水;以及一氣體輸送與移除系統,包含一控制器,其容許i)該蝕刻室曝露於該第二源供應之水蒸氣,及ii)於水蒸氣存在下以該第一源供應之氣相化學蝕刻劑蝕刻該結構;且該結構包含一第一材料及一第二材料,其中該第一材料係選自於矽、鉬、鍺、矽鍺、及鎢,該第二材料係二氧化矽或氮化矽,且該第一材料之至少一表面係經曝露,以便可由氣相化學蝕刻劑接觸。
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