TW201541511A - 在鋁電漿設備部件上產生緊密氧化鋁鈍化層 - Google Patents
在鋁電漿設備部件上產生緊密氧化鋁鈍化層 Download PDFInfo
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- TW201541511A TW201541511A TW104109219A TW104109219A TW201541511A TW 201541511 A TW201541511 A TW 201541511A TW 104109219 A TW104109219 A TW 104109219A TW 104109219 A TW104109219 A TW 104109219A TW 201541511 A TW201541511 A TW 201541511A
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- aluminum
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- aluminum component
- component
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 63
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002161 passivation Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 75
- 230000008569 process Effects 0.000 claims abstract description 71
- 238000012545 processing Methods 0.000 claims abstract description 22
- 230000003746 surface roughness Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910016909 AlxOy Inorganic materials 0.000 abstract 2
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 17
- 239000007789 gas Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100227833 Escherichia coli (strain K12) ftnA gene Proteins 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
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- 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3065—Plasma etching; Reactive-ion etching
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C—CHEMISTRY; METALLURGY
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C22/66—Treatment of aluminium or alloys based thereon
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- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
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- H01L21/67069—Apparatus for fluid treatment for etching for drying etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67242—Apparatus for monitoring, sorting or marking
- H01L21/67248—Temperature monitoring
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- H01—ELECTRIC ELEMENTS
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/673—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere using specially adapted carriers or holders; Fixing the workpieces on such carriers or holders
- H01L21/67303—Vertical boat type carrier whereby the substrates are horizontally supported, e.g. comprising rod-shaped elements
- H01L21/67306—Vertical boat type carrier whereby the substrates are horizontally supported, e.g. comprising rod-shaped elements characterized by a material, a roughness, a coating or the like
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- C—CHEMISTRY; METALLURGY
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- 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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- 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
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- C23F1/14—Aqueous compositions
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- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
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- C—CHEMISTRY; METALLURGY
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- 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
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- C23F1/32—Alkaline compositions
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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
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- C23F1/14—Aqueous compositions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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Abstract
用以在鋁部件上產生緊密氧化鋁鈍化層的製程,包括:以去離子水清洗部件達至少1分鐘,乾燥部件達至少1分鐘,以及在低於10℃之溫度下將部件暴露於濃縮硝酸中達1至30分鐘。所述製程也包括:以去離子水清洗部件達至少1分鐘,乾燥部件達至少1分鐘,以及將部件暴露於NH4OH中達1秒至1分鐘。所述製程進一步包括:以去離子水清洗部件達至少1分鐘,以及乾燥部件達至少1分鐘。用於電漿處理系統的部件包括:鋁部件,所述鋁部件塗佈有厚度4奈米至8奈米之AlxOy薄膜,且所述AlxOy薄膜的表面粗糙度比不具有該AlxOy薄膜之該部件的表面粗糙度增加少於0.05微米。
Description
本專利申請案主張於2014年9月15日申請之美國非臨時專利申請案案號14/486,105的優先權,該美國非臨時專利申請案案號14/486,105則主張於2014年3月31日申請之美國專利臨時案案號61/973,077的優先權優惠期。上述兩申請案內容於此合併做為各方面的參考。
本揭露內容屬於半導體製程工程領域。特別地,所揭露的實施例能在鋁電漿設備部件上產生緊密氧化鋁鈍化層,以快速穩定使用此電漿設備部件之電漿處理設備內的蝕刻率。
半導體處理經常使用電漿處理,以蝕刻或清潔半導體晶圓。穩定且受良好控制的電漿處理參數可促進可預測且可再現的晶圓處理。對電漿製程中所涉及的設備及/或材料的某些改變會暫時中斷電漿處理的穩定性。舉例而言,將在電漿蝕刻環境中不穩定的材料導入電漿腔室、切換電漿腔室中
執行的電漿製程、使腔室暴露於與平常不同的氣體或電漿,及/或替換屬於電漿腔室的部件或電漿腔室中的部件,皆可能中斷製程的穩定性。上述狀況中,起初製程會實質上改變,但可隨著時間穩定,例如當被導入的材料從製程腔室中被逐漸清除時,或當製程腔室內的表面塗層與電漿製程條件達成平衡時。
於一具體實施例中,用以在鋁部件上產生氧化鋁鈍化層之製程包括:在低於10℃的溫度下,將鋁部件暴露於具有至少30%濃度的硝酸(HNO3)中達1分鐘至30分鐘之間。
於一具體實施例中,應用於電漿處理系統中之一部件包括塗佈有AlxOy薄膜的鋁部件,所述AlxOy薄膜具有4奈米至8奈米之厚度,且所述AlxOy薄膜的表面粗糙度比不具有該AlxOy薄膜之鋁部件的表面粗糙度增加少於0.05微米。
於一具體實施例中,用以在鋁部件上產生緊密氧化鋁鈍化層之製程包括:在去離子水中清洗鋁部件至少1分鐘,乾燥鋁部件至少1分鐘,以及在低於10℃之溫度下將鋁部件暴露於濃度為至少30%之硝酸(HNO3)中達1至30分鐘。製程也包括在去離子水中清洗鋁部件至少一分鐘,乾燥鋁部件至少1分鐘,以及將鋁部件暴露於氫氧化銨(NH4OH)中達1秒至1分鐘。製程進一步包括在去離子水中清洗鋁部件至少1分鐘,以及乾燥鋁部件至少1分鐘。
其他的實施例及特徵於後續描述中提出,本發明領域的技術人員當可根據本說明書之內容了解本發明的特徵並
實現本發明。本發明之特徵及優點可藉由說明書中所描述之手段、組合以及方法來實現及獲得。
50‧‧‧工件
100‧‧‧電漿處理系統
110‧‧‧殼體
115‧‧‧晶圓介面
120‧‧‧使用者介面
130‧‧‧製程腔室
135‧‧‧晶圓台座
137‧‧‧擴散板
139‧‧‧氣室
140‧‧‧控制器
150‧‧‧電源供應器
155‧‧‧氣體
160‧‧‧真空幫浦
165‧‧‧射頻產生器
170‧‧‧電源
200‧‧‧製程
210、230、245‧‧‧DI水沖洗
215、235、250‧‧‧CDA乾燥
220‧‧‧HNO3冷卻
225‧‧‧HNO3處理
240‧‧‧NH4OH處理
40A、40B‧‧‧Al層
42A、42B‧‧‧AlxOy層
44A、44B‧‧‧Ir層
46A、46B‧‧‧C層
本發明可參照以下圖式連同詳細說明而獲得了解,其中於不同圖式中的相似的部件使用類似的參考標號。應注意的是,為了清楚描述,圖式中的某些部件並不完全依比例繪示。同樣地,為了清楚描述,若多個圖式繪示出同一物件,僅其中特定的圖式對該物件進行標示。
第1圖繪示根據一具體實施例之電漿處理系統的主要元件。
第2圖描述用來在鋁電漿設備部件上產生緊密氧化鋁鈍化層的示範性製程。
第3A圖及第3B圖為在相近倍率下的掃描式電子顯微鏡(SEM)照片,兩圖分別顯示在一具體實施例中,於相似的製程條件下以稀釋及濃縮硝酸(HNO3)處理後的鋁表面。
第4A圖及第4B圖為在相近倍率下的穿透式電子顯微鏡(TEM)照片,兩圖分別顯示在一具體實施例中,以先前已知之最佳方法清潔後的鋁表面之剖面切片,所述先前已知之最佳方法包括以稀釋HNO3處理以及於室溫下以濃縮HNO3處理。
第5A圖及第5B圖分別顯示在一具體實施例中,於不同溫度及時間下以高濃縮(69%)的HNO3處理的鋁表面的一系列SEM照片。
第6A至第6H圖為相同倍率下的SEM照片,各圖
顯示在多個實施例中,於室溫(RT)或低溫、且於短時間或長時間下,以濃縮或高濃縮HNO3處理後的鋁表面。
第7圖係繪示在一具體實施例中,經處理及未處理之鋁樣本的表面粗糙度結果的長條圖,表面粗糙度係由雷射顯微鏡技術量測而得。
第8A圖及第8B圖係繪示於多個具體實施例中,分別以稀釋HNO3及濃縮HNO3處理後之電漿部件之製程穩定度結果之圖表。
第1圖概要地繪示根據一具體實施例之電漿處理系統100的主要元件。系統100被描繪為單晶圓或半導體晶圓電漿處理系統,但對本領域的技術人員而言,本文所述之技術及原則明顯地可應用於任何類型之工件(即,不一定是晶圓或半導體的物件)之處理系統。處理系統100包括殼體110,殼體110可供晶圓介面115、使用者介面120、製程腔室130、控制器140以及一或多個電源供應器150所用。製程腔室130包括一或多個晶圓台座135,晶圓介面115可將工件50(如半導體晶圓,但也可為其他類型的工件)置於晶圓台座135之上以進行製程。(多種)氣體155可經由氣室139以及擴散板137而被引入製程腔室130中,且射頻產生器(RF Gen)165提供功率以於製程腔室130中點燃電漿。晶圓台座135的表面、製程腔室130的側壁及底面和擴散板137皆為可明顯影響系統100之製程特性的表面。特別是擴散板137可形成很多小孔穿過擴散板137,以平均地散佈氣體及/或電漿於製程腔室
130中,而這些小孔之側壁的表面化學效應可能是顯著的。
以舉例方式列出作為系統100的部份的元件,但並未詳盡地列出所有元件。為了清楚說明,許多其他可能的元件並未繪示於圖中,例如壓力及/或流量控制器;氣體或電漿歧管或散佈裝置;離子抑制板;電極、磁芯及/或其他電磁裝置;機械、壓力、溫度、化學、光學及/或電子感測器;晶圓或其他工件操作機制;觀察及/或其他存取埠(access port)等。為了清楚說明,系統100內部元件的內連接及協同作用同樣未繪示於圖中。除了射頻產生器165及氣體155之外,其他代表性設施如真空幫浦160及/或通用的電源170也可連接至系統100。如同系統100內所示之元件,顯示為連接到系統100的設施為說明性的而非徹底詳盡的,其他類型的設施也可連接至系統100,例如加熱或冷卻流體、壓縮空氣、網路能力、廢料處理系統等,但為了清楚說明,同樣未繪示於圖中。類似地,儘管上述說明提及電漿於製程腔室130中被點燃,下文討論到的原理可被對等地應用於所謂「下游(downstream)」或「遠端(remote)」電漿系統,其於第一位置處產生電漿並致使電漿及/或電漿反應產物移動至第二位置以進行製程。
某些電漿製程對電漿腔室內的表面狀況敏感。於半導體製程的狀況中,對製程穩定性以及均勻度的需求會隨著元件的幾何形狀縮減以及晶圓尺寸增加而加劇。新設備(或有任何腔室部件被替換的設備)可能需要明顯的停工期,以藉模擬製程來調整腔室,所謂模擬製程意指在未暴露實際工件的狀況下進行典型的電漿製程,直到達成可接受的製程穩定性
為止。
對腔室表面狀況非常敏感的電漿製程之一為以三氟化氮(NF3)及氧化氮(N2O)氣體形成之電漿蝕刻薄氮化矽(Si3N4)層。電漿腔室部件,例如第1圖之晶圓台座135、腔室130的側壁及底面、以及擴散板137,可由鋁製成,且可塗佈有氧化鋁薄層(一般以AlxOy表示,通常接近Al2O3,但本揭露內容之範疇也可思及並考慮氧化鋁化學計量上的變異)。新的鋁部件可被清潔且受到稀釋的硝酸(HNO3)混合物處理而產生氧化鋁層,此步驟可以放置鋁部件以接觸浸泡在HNO3中之墊片而達成。當HNO3用於任何類型的製程時,為了安全操作起見,通常會使用稀釋型態。
於本文所述之具體實施例中,可使用濃縮HNO3而非稀釋HNO3,來產生電漿腔室部件的氧化鋁層。本文所用之「高濃縮(highly concentrated)」HNO3代表具有60重量%至100重量%之濃度的HNO3,而本文所用之「濃縮(concentrated)」HNO3(包含高濃縮HNO3)則代表具有30重量%至100重量%之濃度的HNO3。雖然操作濃縮HNO3時須小心謹慎,但相較於使用稀釋HNO3,本發明之實施例可利用濃縮HNO3於鋁部件上提供更緻密且少孔的AlxOy層,因此可將氮化物電漿蝕刻環境中所需之調節時間最小化。亦咸信,將鋁部件浸泡於濃縮HNO3而非使浸泡過HNO3的墊片接觸該部件,可有利於在暴露的Al表面(包括在裂縫、孔洞等處之Al表面)上產生緊密、平滑且均勻的AlxOy層。也發現濃縮HNO3比其它酸及/或氧化物能提供更緊密且更平滑的氧化鋁層,所
述其它酸及/或氧化物如H2O2、HCl、HF、HNO3+HF、H2SO4、HCl+HNO3及NH4OH。
亦咸信在低溫下進行HNO3處理達一段相對短的時間可限制HNO3的解離(如4HNO3=>2H2O+4NO2+O2),進一步藉由抑制H2O對原始鋁表面的攻擊來促進緊密(亦即,密集)且無孔的AlxOy層。既然在合理的製程時間中可達成的AlxOy層的厚度並未改變太多(5至6奈米厚度的AlxOy層),以濃縮HNO3處理之鋁表面可維持與其初始狀況差不多的平滑度,而非如以稀釋HNO3處理而觀測到之較粗糙的鋁表面。咸信,最小化表面粗糙度是鋁部件所暴露之電漿製程的快速穩定的關鍵,因為表面粗糙度在AlxOy層中表現出變異,而這些變異會與電漿製程交互作用直到變異被夷平為止。例如,在表面突出或凹陷處的AlxOy中之初始局部薄點及/或空隙可與電漿交互作用,直至的AlxOy層達到至少數奈米厚度。咸信,本文的實施例能產生先前在鋁部件上未出現的表面拋光度(surface finish),亦即,產生緊密AlxOy薄膜,該緊密AlxOy薄膜所具有的淨表面粗糙度比該薄膜所存在於之鋁部件增加少於0.05奈米。現將揭露使用濃縮HNO3產生緊密AlxOy層的具體實施例、製程結果及其所產生的經鈍化部件的實例,及經鈍化部件的快速製程穩定效果。
第2圖描述用來在鋁電漿設備部件上產生緊密氧化鋁鈍化層的示範性製程200。製程200可被用在,例如,新的或已被處理而移除先前塗層之鋁部件上。製程200的某些部
份可與示範性製程200所顯示的彼等部份以相異的方式執行,如進一步描述於下文。
製程200始於以去離子(DI)水沖洗鋁部件達5分鐘(210),接著於乾淨的乾空氣(clean dry air,CDA)中乾燥鋁部件達5分鐘(215)。當步驟210及215進行時,於一個可選擇的步驟220中,將濃縮或高濃縮HNO3浴冷卻至低溫(例如,低於10℃)。於一些具體實施例中,所述浴有利地為至少60%的HNO3,以將H2O對形成之AlxOy層的影響最小化。於某些具體實施例中,所述浴有利地冷卻至5℃以下,以最小化AlxOy層的表面粗糙度,然而在其他具體實施例中,HNO3浴也可處於室溫下,以最小化用來冷卻HNO3浴之設備及功率需求。鋁部件接著接受HNO3處理達1至30分鐘(225),更有利的是約1至15分鐘,接著以另一去離子(DI)水沖洗達1至30分鐘(230),更有利的是大約5分鐘,並於乾淨的乾空氣中乾燥達1至30分鐘(235),更有利的是大約5分鐘。HNO3處理可成長約4至8奈米厚度的AlxOy,典型的為約5至6奈米,同時不會使鋁部件的表面粗糙度比其原始粗糙度增加超過0.05微米。其次,鋁部件被暴露於氫氧化銨(NH4OH)達1秒至1分鐘(240),更有利的是約1至5秒,以中和任何殘餘的HNO3。暴露於NH4OH後接著以最終的去離子(DI)水清洗達1至30分(245),更有利的是大約5分鐘,並於乾淨的乾空氣中乾燥達1至30分鐘(250),更有利的是大約5分鐘。
對習知技藝者而言,製程200的多種替代及重組是顯而易見的,且這些替代及重組均可被視為落入本揭露內容
的範疇內。上述替代及重組的一些例子為省略最初的去離子(DI)水清洗及乾淨的乾空氣(CDA)乾燥步驟210與215;以氮氣(N2)或其他相關的惰性氣體取代乾淨的乾空氣(CDA)進行任一乾淨的乾空氣(CDA)乾燥步驟215、235、250;以加熱過的乾淨的乾空氣(CDA)(或其他相關的惰性氣體)來加強乾燥;省略乾淨的乾空氣(CDA)乾燥步驟215及/或235,而由之前的去離子(DI)水沖洗直接進入之後的化學步驟225或240,及/或縮短或加長去離子(DI)水清洗或乾淨的乾空氣(CDA)乾燥步驟。
以下揭露鋁電漿設備部件及/或鋁試片以不同稀釋度、溫度以及次數的HNO3進行處理的例子。
第3A圖及第3B圖為在相同倍率下的掃描式電子顯微鏡(SEM)照片,兩圖分別顯示於相似的製程條件下以稀釋及濃縮HNO3處理後的Al表面。第3A圖顯示以稀釋HNO3處理後的Al表面明顯地比以濃縮HNO3處理後的Al表面(第3B圖)更粗糙。
第4A圖及第4B圖為在相近倍率下的穿透式電子顯微鏡(TEM)照片,兩圖分別顯示以先前已知之最佳方法(包含以稀釋HNO3處理)清潔後之Al表面的剖面切片(第4A圖),以及於室溫下以濃縮HNO3清潔後的Al表面之剖面切片(第4B圖)。如第4A圖及第4B圖所示,各別的層40A及40B為下方的鋁,層42A及42B為藉由個別的HNO3處理而形成之AlxOy。進一步的層44A及44B為銥(iridium),且46A及46B
為用於TEM試片製備的碳層。於各層42A及42B中僅測量超過5奈米厚度的AlxOy層。
第5A圖及第5B圖分別顯示在1萬倍的倍率下原始擷取的一系列SEM照片,顯示於不同溫度及不同時間下以高濃縮(69%)的HNO3處理之鋁表面。第5A圖顯示於從約5℃至約60℃的溫度範圍內進行處理的鋁表面的SEM照片,由圖中可從視覺上評估隨著溫度增加會得到較低緊密度/較粗糙的AlxOy層。SEM照片係根據視覺評估(visual evaluation)並根據HNO3處理溫度來排列,然而沿著溫度及緊密度之方向上的排列並未依照比例尺定位。第5B圖顯示以5分鐘至400分鐘的範圍內之時間進行處理之Al表面的SEM照片,由圖中可從視覺上評估隨著溫度增加會得到較低緊密度/較粗糙的AlxOy層。SEM照片係根據對緊密度的視覺評估並根據HNO3處理時間來排列;再次地,沿著時間及緊密度之方向上的排列並未依照比例尺定位。
第6A至第6H圖為相同倍率下的SEM照片,各圖顯示於室溫或低溫(例如低於10℃)、短時間(例如5至25分鐘)或長時間(例如90至150分鐘),以及以濃縮或高濃縮HNO3處理後的Al表面。於第6A圖至第6H圖所顯示之表面形貌中,以長時間處理的樣本明顯地比以短時間在同樣條件下處理的樣本更粗糙,於室溫下處理的樣本比於低溫下以同樣條件處理的樣本更粗糙,並且以濃縮HNO3處理的樣本比以高濃縮HNO3於同樣條件下處理的樣本更粗糙。
第7圖係繪示使用雷射顯微鏡測量的經處理及未處
理之Al樣本的表面粗糙度結果的長條圖。所有經處理的樣本皆是以HNO3在低溫(例如低於10℃)下進行處理。以高濃縮HNO3處理過的鋁樣本的表面粗糙度相當接近於未處理的鋁,而以濃縮HNO3及稀釋HNO3處理過的鋁樣本的表面粗糙度逐步地變高。以濃縮HNO3及高濃縮HNO3處理過的鋁樣本的表面粗糙度比未處理的樣本的表面粗糙度增加少於0.05微米。咸信,先前未曾製造出具有約5奈米厚度之AlxOy層,且此AlxOy層的表面粗糙度比未處理之部件的表面粗糙度增加少於0.05微米的鋁部件。
第8A圖及第8B圖係繪示分別以稀釋HNO3及濃縮HNO3處理之電漿部件之製程穩定度結果的作圖。就第8A圖而言,根據先前製程進行處理的鋁部件被安裝於雙腔室電漿處理系統的兩個製程腔室(兩「側(side)」)內。接著透過運作典型的電漿處理配方之製程循環來使腔室循環,以取得如第8圖所示之資料。儘管一側腔室持續地比另一側腔室蝕刻稍多的量,被蝕刻的量顯著的改變直到約3000次製程循環為止,接著穩定於目標蝕刻量附近。就第8B圖而言,根據第3圖之製程200處理的Al部件被安裝於雙腔室電漿處理系統的兩個製程腔室內。接著透過與針對第8A圖所示的資料相同之製程循環來使腔室循環。間隔測量在相同的標準製程條件下被蝕刻的氮化矽的量,獲得第8B圖所示之資料。在僅約25次製程循環後便可見到被蝕刻的量在目標蝕刻量附近相對較一致,並具有較佳的側對側匹配(side-to-side matching)。
有了上述的多個具體實施例,習知技藝者可認知到
在不偏離本發明之精神下有各種修正、替代結構以及等效物可被採用。此外,未描述已為周知的製程及元件,以避免不必要地混淆本發明。據此,以上敘述不應被當作是本發明的範圍之限制。
當提供一範圍的數值時,除非文本中另外清楚指明,應知亦具體揭示介於該範圍的上下限值之間各個區間值至下限值單位的十分之一。亦涵蓋了所陳述數值或陳述範圍中之區間值以及與陳述範圍中任何另一陳述數值或區間值之間的每個較小範圍。該等較小範圍的上限值與下限值可獨立包含或排除於該範圍中,且各範圍(其中,在該較小範圍內包含任一個極限值、包含兩個極限值,或不含極限值)皆被本發明內所陳述之範圍涵蓋,除非在該陳述的範圍中有特別排除之限制。在所陳述之範圍包括極限值的一者或兩者之處,該範圍也包括該些排除其中任一者或兩者被包括的極限值的範圍。
本文及隨附申請專利範圍中所使用,除非本文另有明確指定,否則單數形式「一(a)」、「一(an)」及「該(the)」包括複數指示物。因此,例如,參照「一製程」包括複數個該等製程,且參照「該電極」包括參照一或多個電極及習知技藝者熟知之該一或多個電極之等效物,等等。並且,此說明書與以下申請專利範圍中所用的「包含(comprise)」與「包括(include)」等用語是指存在所陳述之特徵、整體、部件或步驟,但該等用語不排除存在或增加一或多種其他特徵、整體、部件、步驟、動作或群組。
50‧‧‧工件
100‧‧‧電漿處理系統
110‧‧‧殼體
115‧‧‧晶圓介面
120‧‧‧使用者介面
130‧‧‧製程腔室
135‧‧‧晶圓台座
137‧‧‧擴散板
139‧‧‧氣室
140‧‧‧控制器
150‧‧‧電源供應器
155‧‧‧氣體
160‧‧‧真空幫浦
165‧‧‧射頻產生器
170‧‧‧電源
Claims (14)
- 一種用以在一鋁部件上產生一緊密氧化鋁鈍化層的製程,包含:在低於10℃的溫度下,將該鋁部件暴露於具有至少30%的濃度之硝酸(HNO3)達1分鐘至30分鐘之間。
- 如請求項1所述之製程,其中該HNO3具有至少60%的濃度。
- 如請求項1所述之製程,其中該HNO3具有5℃或更低的溫度。
- 如請求項1所述之製程,其中該暴露的步驟包含:將該鋁部件浸泡於該HNO3中達1分鐘至15分鐘之間。
- 如請求項1所述之製程,進一步包含:在將該鋁部件暴露於該HNO3之前,以去離子(DI)水清洗該鋁部件並乾燥該鋁部件。
- 如請求項1所述之製程,進一步包含:在將該鋁部件暴露於該HNO3之後,以去離子(DI)水清洗該鋁部件。
- 如請求項6所述之製程,進一步包含:在將該鋁部件暴露於該HNO3並以去離子(DI)水沖洗該鋁部件之後,將該鋁部 件暴露於NH4OH中達1秒至1分鐘之間。
- 如請求項7所述之製程,其中將該鋁部件暴露於NH4OH包含:將該鋁部件浸置於NH4OH中達1至10秒之間。
- 一種用於一電漿處理系統之部件,包含:一鋁部件,該鋁部件塗佈有厚度4奈米至8奈米之一AlxOy薄膜,且該AlxOy薄膜的表面粗糙度比不具有該AlxOy薄膜之該鋁部件的表面粗糙度增加少於0.05微米。
- 一種用以在一鋁部件上產生一緊密氧化鋁鈍化層的製程,包含:於去離子水中清洗該鋁部件達至少1分鐘;乾燥該鋁部件達至少1分鐘;在低於10℃的溫度下,將該鋁部件暴露於具有至少30%的濃度之硝酸(HNO3)中達1分鐘至30分鐘之間;於去離子水中清洗該鋁部件達至少1分鐘;乾燥該鋁部件達至少1分鐘;將該鋁部件暴露於NH4OH中達1秒至1分鐘之間;於去離子水中清洗該鋁部件達至少1分鐘;以及乾燥該鋁部件達至少1分鐘。
- 如請求項10所述之製程,其中該HNO3具有至少60%的濃度。
- 如請求項10所述之製程,其中該HNO3具有5℃或更低的溫度。
- 如請求項10所述之製程,其中該暴露的步驟包含:將該鋁部件浸泡於該HNO3中達1分鐘至15分鐘之間。
- 如請求項10所述之製程,其中將該鋁部件暴露於NH4OH包含:將該鋁部件浸置於NH4OH中達1至10秒之間。
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