TW202030319A - 用於化學機械研磨後(post-cmp)鈷基板之清洗的組合物及方法 - Google Patents
用於化學機械研磨後(post-cmp)鈷基板之清洗的組合物及方法 Download PDFInfo
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- TW202030319A TW202030319A TW108145751A TW108145751A TW202030319A TW 202030319 A TW202030319 A TW 202030319A TW 108145751 A TW108145751 A TW 108145751A TW 108145751 A TW108145751 A TW 108145751A TW 202030319 A TW202030319 A TW 202030319A
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- acid
- ether
- glycol
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- hydroxide
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- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229940057950 sodium laureth sulfate Drugs 0.000 description 1
- 229940054269 sodium pyruvate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
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- 150000003460 sulfonic acids Chemical class 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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- ZOMVKCHODRHQEV-UHFFFAOYSA-M tetraethylphosphanium;hydroxide Chemical compound [OH-].CC[P+](CC)(CC)CC ZOMVKCHODRHQEV-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0042—Reducing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0047—Other compounding ingredients characterised by their effect pH regulated compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3445—Organic compounds containing sulfur containing sulfino groups, e.g. dimethyl sulfoxide
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
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Abstract
本發明揭示一種用於自上面有殘留物及/或污染物之微電子裝置清洗該等殘留物及/或污染物的清洗組合物。該組合物包含至少一種錯合劑、至少一種清洗添加劑、至少一種pH調節劑、水及至少一種氧胺化合物。有利地,該組合物展示含鈷基板之有效清洗及經改良之鈷相容性。
Description
本發明大體上係關於用於自上面有殘留物及/或污染物之微電子裝置清洗該等殘留物及/或污染物的清洗組合物,其中該等組合物具有經改良之鈷相容性。
微電子裝置晶圓用於形成積體電路且包括諸如矽之基板,在基板中區域經圖案化用以沈積具有絕緣、導電或半導電特性之不同材料。
為獲得恰當之圖案化,必須移除用於在基板上形成層之過量材料。此外,為製造功能性且可靠之電路,在後續加工之前製備平整或平坦之微電子晶圓表面很重要。因此,必需移除及/或研磨微電子裝置晶圓之某些表面。
化學機械研磨或平坦化(「CMP」)為一種自微電子裝置晶圓之表面移除材料,且藉由聯合物理方法(諸如磨耗)與化學方法(諸如氧化或螯合)研磨(例如,平坦化)該表面的方法。基本上,CMP涉及將研磨漿料(諸如在水溶液中含有活性化學物質之研磨劑之組合)施加至研磨墊,該研磨墊在移除、平坦化及研磨製程期間磨光微電子裝置晶圓之表面。物理與化學操作之協同組合實現快速、均勻移除。在積體電路的製造中,CMP漿料亦應能夠優先移除包含金屬及其他材料之錯合層之膜,從而可產生用於後續光微影、或圖案化、蝕刻及薄膜處理之高度平坦之表面。在研磨之後獲得在整個晶圓表面中之良好均勻性之一個關鍵為使用針對所存在材料中之每一者具有恰當移除選擇性之CMP漿料。
大多數工藝操作(包括晶圓基板表面製備、沈積、電鍍、蝕刻及化學機械研磨)需要清洗操作以確保微電子裝置產物無將另外有害影響產物之功能或甚至致使微電子裝置產物不可用於其預期功能之污染物。通常,此等污染物之粒子小於0.3 μm。若未移除,則此等殘留物可對例如銅線造成損害或嚴重粗糙化銅金屬化物,以及造成裝置基板上之CMP後經施加之層黏著性不佳。
在本行業中持續需要提供自基板有效地及選擇性地移除各種殘留物(例如CMP後殘留物、刻蝕後殘留物及灰化後殘留物)之組合物及方法,特別是隨著對經改良之裝置效能及減小之裝置尺寸及減小之裝置特徵尺寸的需求增加。組合物及方法應消除粒子及其他污染物,且不腐蝕或以其他方式損害諸如鈷之組分。
本發明大體上係關於用於自上面有殘留物及/或污染物之微電子裝置清洗該等殘留物及/或污染物的組合物及方法。該殘留物可包括CMP後、蝕刻後及/或灰化後殘留物。有利地,本文中所描述之組合物相對於此項技術中先前所描述之組合物展示經改良之鈷相容性。
在一個態樣中,描述一種清洗組合物,該組合物包含至少一種錯合劑、至少一種清洗添加劑、至少一種pH調節劑、水及至少一種氧胺化合物或其鹽。在一些實施例中,該組合物進一步包含至少一種蝕刻劑、至少一種腐蝕抑制劑及/或至少一種還原劑。較佳地,該清洗組合物實質上不含含氟化物源、研磨材料及氫氧化四甲銨。
在另一態樣中,描述自上面有殘留物及污染物之微電子裝置移除該等殘留物及污染物的方法,該方法包含使微電子裝置與清洗組合物接觸足以至少部分地自微電子裝置清洗該等殘留物及污染物的時間,其中該清洗組合物包含至少一種錯合劑、至少一種清洗添加劑、水、至少一種pH調節劑及至少一種氧胺化合物或其鹽。在一些實施例中,該組合物進一步包含至少一種蝕刻劑、至少一種腐蝕抑制劑及/或至少一種還原劑。較佳地,該清洗組合物實質上不含含氟化物源、研磨材料及氫氧化四甲銨。
其它態樣、特徵及優勢將自隨後揭示內容及隨附申請專利範圍更充分地顯而易見。已發現相對於先前技術中之組合物,此類組合物可實現經改良之鈷相容性。此類相容性例如在現代微電子裝置製程中之CMP後清洗中具有相當大的益處。
本發明大體上係關於適用於自上面有殘留物及污染物之微電子裝置移除此類材料的組合物。該等組合物尤其適用於在不損害大部分鈷之情況下自含鈷基板移除CMP後、蝕刻後或灰化後殘留物。
為易於參考,「微電子裝置」對應於半導體基板、平板顯示器、相變記憶體裝置、太陽電池板及其他包括太陽能基板、光伏打及微機電系統(MEMS)之產物,經製造用於微電子應用、積體電路應用或電腦晶片應用。太陽能基板包括但不限於矽、非晶矽、多晶矽、單晶矽、CdTe、硒化銅銦、硫化銅銦及鎵上砷化鎵(gallium arsenide on gallium)。太陽能基板可經摻雜或未經摻雜。應理解,術語「微電子裝置」並不意欲以任何方式限制且包括將最終變為微電子裝置或微電子組件之任何基板。
該微電子裝置可包含含鈷材料。如本文中所使用,「含鈷材料」及「鈷物種」包括包含按材料之總重量計大於50 wt%元素鈷之任何材料。含鈷材料之實例包括但不限於純鈷、氮化鈷(包括包含諸如Ta或Li之額外元素的氮化鈷)、CoP、CoSi、CoW、氧化鈷及氫氧化鈷。熟習此項技術者應理解,用於各種氧化鈷及氮化鈷之化學式可基於鈷離子之氧化態而變化,其中鈷之常見氧化態為-3、-1、+1、+2、+3、+4或+5。
如本文中所使用,「殘留物」對應於在製造微電子裝置期間產生的粒子,該微電子裝置包括但不限於電漿蝕刻、灰化、化學機械研磨、濕式蝕刻及其組合。
如本文所使用,「污染物」對應於存在於CMP漿料中之化學物質、研磨漿液之反應副產物、存在於濕式蝕刻組合物中之化學物質、濕式蝕刻組合物之反應副產物,及為CMP製程、濕式蝕刻、電漿蝕刻或電漿灰化製程之副產物之任何其他材料。常見污染物包括苯并三唑,其通常存在於CMP漿料中。
如本文中所定義,「蝕刻後殘留物」對應於在氣相電漿蝕刻製程(例如,BEOL雙金屬鑲嵌工藝或濕式蝕刻製程)之後所剩餘的材料。蝕刻後殘留物可為有機物、有機金屬、有機矽,或本質上為例如含矽材料之無機物、基於碳之有機材料及諸如氧氣及氟氣之蝕刻氣體殘留物。
如本文中所定義,如本文中所使用之「灰化後殘留物」對應於與用以去除硬化光阻及/或底部抗反射塗層(BARC)材料之氧化或還原電漿灰化之後所剩餘的材料。灰化後殘留物可為有機物、有機金屬、有機矽或本質上為無機物。
如本文中所使用,「CMP後殘留物」對應於來自研磨漿料之粒子,例如含二氧化矽粒子、存在於漿料中之化學物質、研磨漿料之反應副產物、富碳粒子、研磨墊粒子、刷去載粒子、建構粒子之裝備材料、金屬、金屬氧化物、有機殘留物、障壁層殘留物及為CMP製程之副產物之任何其他材料。如本文中所定義,經典型研磨之「金屬」包括銅、鋁及鎢。
如本文中所定義,「反應物或降解產物」包括但不限於由於在表面處之催化、氧化、還原、與組成組分反應或以其他方式聚合而形成之(一或多種)產物或副產物;由於(一或多種)變化或(一或多種)轉化而形成之(一或多種)產物或副產物,在該等變化及轉化中,物質或材料(例如分子、化合物等)與其他物質或材料組合,與其他物質或材料交換組分、分解、重排或以其他方式經化學及/或物理改變,包括前述(一或多種)反應、(一或多種)變化及/或(一或多種)轉化之任何組合中之任一者的(一或多種)中間產物或(一或多種)副產物。應瞭解,反應物或降解產物可具有比原始反應物更大或更小之莫耳質量。
如本文中所使用,「低k介電材料」對應於在分層微電子裝置中用作介電材料的任何材料,其中該材料具有小於約3.5之介電常數。較佳地,低k介電材料包括低極性材料,諸如含矽有機聚合物、含矽雜交有機/無機材料、有機矽酸鹽玻璃(OSG)、TEOS、氟化矽酸鹽玻璃(FSG)、二氧化矽及摻碳氧化物(CDO)玻璃。應瞭解低k介電材料可具有不同密度及不同孔隙率
如本文中所定義,術語「障壁材料」對應於此項技術中用以密封金屬線(例如,銅互連件)以使該金屬(例如,銅)向介電材料之擴散降至最低之任何材料。較佳障壁層材料包括鉭、鈦、釕、鉿、鎢、鈷以及前述金屬中之任一者之氮化物及矽化物。
如本文中所使用,「錯合劑」包括由熟習此項技術者理解為錯合劑、螯合劑及/或鉗和劑之彼等化合物。錯合劑將與待使用本文中所描述之組合物移除之金屬原子及/或金屬離子化學組合或以物理方式夾持該金屬原子及/或金屬離子。
如本文中所使用,「含氟化合物」對應於以離子方式鍵結至另一原子之氟離子(F-)的鹽或酸化合物。
「實質上不含」在本文中定義為小於2 wt.%、小於1 wt.%、小於0.5 wt.%或小於0.1 wt.%。在一個實施例中,「實質上不含」對應於零百分比,指示組合物不含特定組分。
如本文中所使用,「約」意欲對應於所陳述值之±5%。
如本文中所使用,用於自上面有殘留物及污染物之微電子裝置清洗該等殘留物及污染物之「適合性」對應於自微電子裝置至少部分移除該等殘留物/污染物。清洗功效由在微電子裝置上之物體之減少來評定。舉例而言,可使用原子力顯微鏡來進行清洗前分析及清洗後分析。樣品上之粒子可記錄為像素範圍。直方圖(例如,Sigma Scan Pro)可應用於以特定強度(例如,231-235)過濾像素及計數粒子之數目。粒子減少可使用以下計算:
值得注意,清洗功效之測定方法僅提供為實例且並不意欲受限於該實例。可替代地,清洗功效可視為由粒子物質所覆蓋之全部表面的百分比。舉例而言,可對AFM進行編程以執行z平面掃描以在某一高度臨限值以上鑑定所關注之表面形貌區域,且隨後計算由所關注之該等區域覆蓋之總表面面積。熟習此項技術者將容易理解,由清洗後所關注之該等區域覆蓋之面積愈小,清洗組合物愈有效。較佳地,使用本文中所述之組合物自微電子裝置移除至少75%之殘留物/污染物,更佳地移除至少90%、甚至更佳地移除至少95%且最佳地移除至少99%之殘留物/污染物。
如下文更充分地描述,本文所述之組合物可以廣泛多種特定調配物形式體現。
在所有此類組合物中,其中參考重量百分比範圍(包括零下限)論述組合物之特定組分,應理解該等組分可存在或不存在於組合物之各種特定實施例中,且在存在此類組分之實例中,按採用此類組分之組合物的總重量計,其可以低至0.001重量百分比之濃度存在。
貫穿本說明書之實施方式及申請專利範圍,字語「包含(comprise)」及「含有(contain)」以及該等字語之變體,例如「包含(comprising/comprises)」意謂「包括但不限於」且不排除其他組件、整數或步驟。然而,無論在何處使用字語「包含」,亦明確包涵其中將「包含」理解為「由…組成」或「基本上由…組成」之一實施例。
本文中,除非上下文另外要求,否則單數形式包涵複數形式。詳言之,當使用不定冠詞時,除非上下文另外要求,否則本說明書應理解為涵蓋複數及單數。
本發明各態樣之較佳特徵可如結合其他態樣中之任一者所描述。在本申請案之範疇內,明確地預期前述段落中、申請專利範圍中及/或在以下描述及圖式中所闡述之各種態樣、實施例、實例及替代例及詳言之其個別特徵可獨立或以任何組合採用。亦即,除非此類特徵不相容,否則可以任何方式及/或組合來組合所有實施例及/或任何實施例之特徵。
在自微電子裝置移除殘留物材料之前,本文中所描述之清洗組合物可實質上不含或不含含氟化物源、研磨材料、氫氧化四甲銨(TMAH)及其組合。此外,清洗組合物不應固化以形成聚合物固體,例如光阻。如熟習此項技術者易於理解,儘管預期調配物可包括至少一種界面活性劑,但亦預期該等調配物實質上不含界面活性劑。
清洗組合物包含以下組分、由以下組分組成或基本上由以下組分組成:至少一種錯合劑、至少一種清洗添加劑、至少一種pH調節劑、水及至少一種氧胺化合物或其鹽。較佳地,清洗組合物為包含至少50%水之水性清洗組合物。有利地,清洗組合物增加殘留在微電子裝置之經暴露之鈷上的污染物及殘留物(例如苯并三唑、漿料粒子及其他CMP後殘留物)的移除且同時降低經暴露之鈷的腐蝕速率。
在一個較佳實施例中,本發明之清洗組合物包含以下、由以下組成或基本上由以下組成:至少一種錯合劑、至少一種清洗添加劑、至少一種pH調節劑、至少一種氧胺化合物或其鹽及水,其中該清洗組合物按以下重量百分比比率調配:
不論何時組分之濃度在本文中指定時,應理解水可將組合物之平衡量補償至100%。按組合物之總重量計,清洗組合物中之水的量可為至少80 wt%、較佳至少85 wt%、且更佳至少90 wt%。
組分 | 重量百分比 | 較佳重量百分比 |
錯合劑 | 約0.01 wt%至約20 wt% | 約0.1 wt%至約10 wt% |
清洗添加劑 | 約0.01 wt%至約20 wt% | 約0.1 wt%至約10 wt% |
pH 調節劑 | 約0.1 wt%至約10 wt% | 約1 wt%至約5 wt% |
氧胺化合物或鹽 | 約0.01 wt%至約25 wt% | 約0.1 wt%至約10 wt% |
本發明之清洗組合物包含至少一種錯合劑(金屬螯合劑、金屬錯合劑或金屬鉗合劑)。錯合劑將與待使用本文中所描述之組合物移除之金屬原子及/或金屬離子化學組合或以物理方式夾持該金屬原子及/或金屬離子。適合地,組合物可包含由複數個錯合劑組成之錯合劑組分。說明性錯合劑可包括具有通式NR1
R2
R3
之物種,其中R1
、R2
及R3
可彼此相同或不同且係選自由以下組成之群:如上文所定義之氫、直鏈或分支鏈C1
-C6
烷基(例如甲基、乙基、丙基、丁基、戊基及己基)、直鏈或分支鏈C1
-C6
羥基烷基(例如羥基甲基、羥基乙基、羥基丙基、羥基丁基、羥基戊基及羥基己基)、及直鏈或分支鏈C1
-C6
羥基烷基之C1
-C6
烷基醚。最佳地,R1
、R2
及R3
中之至少一者為直鏈或分支鏈C1-
C6
羥基烷基。實例包括(但不限於)烷醇胺,諸如胺基乙基乙醇胺、N-甲基胺基乙醇、胺基乙氧基乙醇、二甲基胺基乙氧基乙醇、二乙醇胺、N-甲基二乙醇胺、單乙醇胺(MEA)、三乙醇胺(TEA)、異丙醇胺、二異丙醇胺、胺基丙基二乙醇胺、N,N-二甲基丙醇胺、N-甲基丙醇胺、1-胺基-2-丙醇、2-胺基-1-丁醇、異丁醇胺、三伸乙基二胺、其他C1
-C8
烷醇胺及其組合。當胺包括烷基醚組分時,胺可視為烷氧基胺,例如1-甲氧基-2-胺基乙烷。
可替代地或除NR1
R2
R3
胺以外,錯合劑亦可為多官能胺包括但不限於:4-(2-羥基乙基)嗎啉(HEM)、1,2-環己二胺-N,N,N',N'-四乙酸(CDTA)、乙二胺四乙酸(EDTA)、間二甲苯二胺(MXDA)、亞胺二乙酸(IDA)、2-(羥基乙基)亞胺二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、尿酸、丙胺酸、精胺酸、天冬醯胺、天冬胺酸、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、苯丙胺酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸及其組合。
替代地,或除前述錯合劑以外,額外錯合劑可包括膦酸酯(例如1-羥基亞乙基-1,1-二膦酸(HEDP)、1,5,9-三氮雜環十二烷-N,N',N''-參(亞甲基膦酸)(DOTRP)、1,4,7,10-四氮雜環十二烷-N,N,N'',N'''-肆(亞甲基膦酸)(DOTP)、氮基參(亞甲基)三膦酸、二伸乙基三胺五(亞甲基膦酸)(DETAP)、胺基三(亞甲基膦酸)、雙(伸己基)三胺伸戊基膦酸、1,4,7-三氮雜環壬烷-N,N',N''-參(亞甲基膦酸(NOTP)、羥基乙基二膦酸酯、氮基參(亞甲基)膦酸、2-膦醯基-丁烷-1,2,3,4-四甲酸、羧基乙基膦酸、胺基乙基膦酸、草甘膦、乙二胺四(亞甲基膦酸)苯基膦酸、其鹽及其衍生物)及/或羧酸(例如,草酸、丁二酸、順丁烯二酸、蘋果酸、丙二酸、己二酸、鄰苯二甲酸、檸檬酸、檸檬酸鈉、檸檬酸鉀、檸檬酸銨、1,2,3-丙三羧酸、二羥甲基丙酸、三羥甲基丙酸、酒石酸、葡糖醛酸、2-羧基吡啶)及/或諸如試鈦靈之磺酸(4,5-二羥基-1,3-苯二磺酸二鈉鹽)。例如,至少一種錯合劑可包含選自由單乙醇胺、三乙醇胺、硫酸、檸檬酸及其組合組成之群的物種。
按清洗組合物之總重量計,清洗組合物中之一或多種錯合劑的量在約0.01 wt%至約20 wt%之範圍內。較佳地,按清洗組合物之總重量計,錯合劑以約0.01 wt%至約10 wt%的量存在,且更佳以約0.01 wt%至約5 wt%的量存在。
本發明之清洗組合物包含至少一種清洗添加劑,其可包括各種溶劑、水溶性聚合物及界面活性劑。適合地,組合物可包含由複數種清洗添加劑組成之清洗添加劑組分。說明性清洗添加劑包括但不限於,2-吡咯啶酮、1-(2-羥基乙基)-2-吡咯啶酮(HEP)、甘油、1,4-丁二醇、伸丁基碸(環丁碸)、二甲碸、乙二醇、丙二醇、二丙二醇、四乙二醇二甲醚、二乙二醇二甲醚、甲基異丁基酮、甲基乙基酮、丙酮、異丙醇、辛醇、乙醇、丁醇、甲醇、異佛爾酮、二醇醚(例如二乙二醇單甲醚、三乙二醇單甲醚、二乙二醇單乙醚、三乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單丁醚(DEGBE)、三乙二醇單丁醚(TEGBE)、乙二醇單己醚(EGHE)、二乙二醇單己醚(DEGHE)、乙二醇苯醚、二乙二醇苯醚、六乙二醇單苯醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二丙二醇二甲醚、二丙二醇乙醚、丙二醇正丙醚、二丙二醇正丙醚(DPGPE)、三丙二醇正丙醚、丙二醇正丁醚(諸如DOWANOL PnB)、二丙二醇正丁醚、三丙二醇正丁醚、二丙二醇苯醚、丙二醇苯醚(PPh,諸如DOWANOL PPh)、4-甲基-2-戊酮、2,4-二甲基-3-戊酮、環己酮、5-甲基-3-庚酮、3-戊酮、5-羥基-2-戊酮、2,5-己二酮、4-羥基-4-甲基-2-戊酮、丙酮、丁酮、2-甲基-2-丁酮、3,3-二甲基-2-丁酮、4-羥基-2-丁酮、環戊酮、2-戊酮、3-戊酮、1-苯基乙酮、苯乙酮、二苯甲酮、2-己酮、3-己酮、2-庚酮、3-庚酮、4-庚酮、2,6-二甲基-4-庚酮、2-辛酮、3-辛酮、4-辛酮、二環己基酮、2,6-二甲基環己酮、2-乙醯基環己酮、2,4-戊二酮、薄荷酮、二甲亞碸(DMSO)、二甲基甲醯胺(DMF)、N-甲基吡咯啶酮、N-乙基吡咯啶酮、碳酸伸乙酯、碳酸伸丙酯、塞里尼(cyrene)、二甲基伸乙基脲及其組合。
替代地或另外,該清洗添加劑可包括水溶性聚合物或表面活性劑,其包括例如,甲基丙烯酸均聚物及與例如丙烯醯胺基甲基丙烷磺酸及順丁烯二酸之共聚物;順丁烯二酸/乙烯基醚共聚物;聚(乙烯吡咯啶酮)/乙酸乙烯酯;均聚物,諸如膦酸化聚乙二醇寡聚物、聚(丙烯酸)(PAA)、聚(丙烯醯胺)、聚(乙酸乙烯酯)、聚(乙二醇)(PEG)、聚(丙二醇)(PPG)、聚(苯乙烯磺酸)、聚(乙烯基磺酸)、聚(乙烯基膦酸)、聚(乙烯基磷酸)、聚(伸乙亞胺)、聚(伸丙亞胺)、聚烯丙胺、聚氧化乙烯(PEO)、聚乙烯吡咯啶酮(PVP)、聚(乙烯醇)、親水性水溶性或分散性聚氨酯,聚(乙二醇丙烯酸酯)、聚(乙二醇甲基丙烯酸脂)、PPG-PEG-PPG嵌段共聚物、PEG-PPG-PEG嵌段共聚物及其組合。
替代地或另外,至少一種清洗添加劑可為界面活性劑,其包括但不限於陰離子、非離子、陽離子及/或兩性離子界面活性劑。實例包括褐藻酸及其鹽;羥基或羧基烷基纖維素;硫酸葡聚糖及其鹽;聚(半乳糖醛酸)及其鹽;(甲基)丙烯酸及其鹽、順丁烯二酸、順丁烯二酸酐、苯乙烯磺酸及其鹽、乙烯基磺酸及其鹽、烯丙基磺酸及其鹽、丙烯醯胺基丙基磺酸及其鹽之均聚物;(甲基)丙烯酸及其鹽、順丁烯二酸、順丁烯二酸酐、苯乙烯磺酸及其鹽、乙烯基磺酸及其鹽、烯丙基磺酸及其鹽、丙烯醯胺基丙基磺酸及其鹽之共聚物;聚葡萄胺糖;陽離子澱粉;聚離胺酸及其鹽;氯化二烯丙基二甲銨(DADMAC)、溴化二烯丙基二甲銨、硫酸二烯丙基二甲銨、磷酸二烯丙基二甲銨、氯化二甲基烯丙基二甲銨、氯化二乙基烯丙基二甲銨、氯化二烯丙基二(β-羥基乙基)銨、氯化二烯丙基二(β-乙氧基乙基)銨、二甲基胺基乙基(甲基)丙烯酸酯酸加成鹽及四級鹽、二乙基胺基乙基(甲基)丙烯酸酯酸加成鹽及四級鹽、7-胺基-3,7-二甲基辛基(甲基)丙烯酸酯酸加成鹽及四級鹽、N,N'-二甲基胺基丙基丙烯醯胺酸加成鹽及四級鹽、烯丙胺、二烯丙胺、乙烯胺、乙烯吡啶之均聚物;及氯化二烯丙基二甲銨(DADMAC)、溴化二烯丙基二甲銨、硫酸二烯丙基二甲銨、磷酸二烯丙基二甲銨、氯化二甲基烯丙基二甲銨、氯化二烯丙基二甲銨、氯化二烯丙基二(β-羥基乙基)銨、氯化二烯丙基二(β-乙氧基乙基)銨、二甲基胺基乙基(甲基)丙烯酸酯酸加成鹽及四級鹽、二乙基胺基乙基(甲基)丙烯酸酯酸加成鹽及四級鹽、7-胺基-3,7-二甲基辛基(甲基)丙烯酸酯酸加成鹽及四級鹽、N,N'-二甲基胺基丙基丙烯醯胺酸加成鹽及四級鹽、烯丙胺、二烯丙胺、乙烯胺、乙烯吡啶之共聚物;椰油二甲基羧甲基甜菜鹼;月桂基二甲基羧甲基甜菜鹼;月桂基二甲基-α-羧乙基甜菜鹼;十六烷基二甲基羧甲基甜菜鹼;月桂基-雙-(2-羥基乙基)羧甲基甜菜鹼;硬脂基-雙-(2-羥基丙基)羧甲基甜菜鹼;油醯基二甲基-γ-羧丙基甜菜鹼;月桂基-雙-(2-羥基丙基)α-羧乙基甜菜鹼;椰油二甲基磺丙基甜菜鹼;硬脂基二甲基磺丙基甜菜鹼;月桂基-雙-(2-羥基乙基)磺丙基甜菜鹼;十二烷基硫酸鈉(SDS);Surfynol 104、磺基丁二酸二辛酯鈉鹽;月桂基醚硫酸鈉;聚乙二醇分支鏈-壬基苯基醚硫酸銨鹽;2-十二烷基-3-(2-磺酸根基苯氧基)二鈉;PEG25-PABA;聚乙二醇單-C10-16-烷基醚硫酸鈉鹽;(2-N-丁氧基乙氧基)乙酸;十六烷基苯磺酸;氫氧化鯨蠟基三甲銨;氫氧化十二烷基三甲銨;氯化十二烷基三甲銨;氯化鯨蠟基三甲銨;氯化N-烷基-N-苄基-N,N-二甲基胺;十二烷基胺;聚氧乙烯月桂基醚;十二烯基丁二酸單二乙醇醯胺;乙二胺肆(乙氧基化物-嵌段-丙氧基化物);及其組合。
尤其清洗添加劑包括但不限於羥基丙基纖維素、羥基乙基纖維素、羧甲基纖維素、羧甲基纖維素鈉(NaCMC)、十二烷基硫酸鈉(SDS);十二烷基硫酸銨、十二烷基硫酸鉀、羧甲基纖維素銨、羧甲基纖維素鉀、海藻酸銨、海藻酸鉀、海藻酸鹽鈣、Surfynol 104、聚乙烯吡咯啶酮(PVP)、使用N-乙烯吡咯啶酮單體製得之任何聚合物、聚(乙烯醇)、聚丙烯酸酯及聚丙烯酸酯之類似物、聚胺基酸(例如聚丙胺酸、聚白胺酸、聚甘胺酸等)、聚醯胺羥基胺基甲酸酯、聚內酯、聚丙烯醯胺、三仙膠、聚葡萄胺糖、聚氧化乙烯、聚乙烯醇、聚乙酸乙烯酯、聚丙烯酸、聚乙亞胺、諸如山梨醇酯及木糖醇之糖醇、去水山梨醇之酯、去水山梨醇之酯、諸如TERGITOL之二級醇乙氧基化物及其組合。
按清洗組合物之總重量計,清洗組合物中之清洗添加劑的量在約0.01 wt%至約20 wt%之範圍內。較佳地,按清洗組合物之總重量計,清洗添加劑以約0.1 wt%至約10 wt%的量存在,且更佳以約0.5 wt%至約5 wt%的量存在。
本發明之清洗組合物包含至少一種pH調節劑,其用於將組合物之pH升高或降低至目標值。儘管pH調節劑可包括酸及/或鹼,較佳地pH調節劑為鹼且用於提昇清洗組合物之pH。說明性鹼包括但不限於鹼金屬氫氧化物(例如,LiOH、KOH、RbOH、CsOH)、鹼土金屬氫氧化物(例如Be(OH)2
、Mg(OH)2
、Ca(OH)2
、Sr(OH)2
、Ba(OH)2
)、氫氧化銨(亦即,氨)及具有式NR1
R2
R3
R4
OH之氫氧化四烷銨化合物,其中R1
、R2
、R3
及R4
可彼此相同或不同且選自由以下組成之群:氫、直鏈或分支鏈C1
-C6
烷基(例如甲基、乙基、丙基、丁基、戊基及己基)、C1
-C6
羥基烷基(例如羥基甲基、羥基乙基、羥基丙基、羥基丁基、羥基戊基及羥基己基)、及經取代之或未經取代之C6
-C10
芳基(例如苄基)。可使用可商購之氫氧化四烷基銨包括氫氧化四甲銨(TMAH)、氫氧化四乙基銨(TEAH)、氫氧化四丙基銨(TPAH)、氫氧化四丁基銨(TBAH)、氫氧化三丁基甲銨(TBMAH)、氫氧化苄基三甲銨(BTMAH)、氫氧化膽鹼、氫氧化乙基三甲基銨、氫氧化參(2-羥基乙基)甲銨、氫氧化二乙基二甲基銨及其組合。
替代地或另外,該pH調節劑可為具有式(PR1
R2
R3
R4
)OH之四級鹼,其中R1
、R2
、R3
及R4
可彼此相同或不同且選自由以下組成之群:氫、直鏈C1
-C6
烷基(例如甲基、乙基、丙基、丁基、戊基及己基)、分支鏈C1
-C6
烷基、C1
-C6
羥基烷基(例如羥基甲基、羥基乙基、羥基丙基、羥基丁基、羥基戊基及羥基己基)、經取代之C6
-C10
芳基、未經取代之C6
-C10
芳基(例如苄基)及其任何組合,諸如氫氧化四丁基鏻(TBPH)、氫氧化四甲基鏻、氫氧化四乙基鏻、氫氧化四丙基鏻、氫氧化苄基三苯基鏻、氫氧化甲基三苯基鏻、氫氧化乙基三苯基鏻、氫氧化正丙基三苯基鏻。
所添加(一或多種)pH調節劑的量取決於所需pH,如本文中所揭示及如熟習此項技術者所理解。例如,按清洗組合物之總重量計,pH調節劑可以約0.1 wt%至約10 wt%的量存在,且更佳以約1 wt%至約5 wt%的量存在。在一個實施例中,pH調節劑包含KOH。在另一實施例中,pH調節劑包含氫氧化膽鹼。在又另一實施例中,pH調節劑包含氫氧化銨。在另一實施例中,pH調節劑包含本文中所枚舉之至少一種鹼金屬氫氧化物及至少一種額外氫氧化物。在另一實施例中,pH調節劑包含KOH及至少一種本文中所枚舉之額外氫氧化物。在再一實施例中,pH調節劑包含KOH及氫氧化膽鹼及氫氧化銨中之至少一者。
本文中所描述之清洗組合物之pH可視目標應用而變化。在一個實施例中,組合物之pH大於7,且因而可為鹼性水性清洗組合物。對於此實施例,較佳地pH在約10至大於14之範圍內,更佳地在約12至約14之範圍內,且最佳在約13至14之範圍內。熟習此項技術者應理解,在稀釋後,諸如藉由形成下文所描述之濃度及隨後添加水,清洗組合物之pH將降低至約10至約12之範圍內。
本文中所描述之清洗組合物包含至少一種氧胺化合物或其鹽。詳言之,氧胺化合物可為羥胺或胺氧基(硝醯基)化合物。例如,組合物可包含至少一種羥胺化合物、至少一種胺氧基化合物或其組合。氧胺化合物原則上可為包括鍵結至氮(N)原子之氧基(諸如-O-或-OH)的任何化合物。在一些情況下,氧胺化合物之鹽形式可更穩定或可易於獲得,其中化合物包括鍵結至氮原子之羥基化(-OM)基團。實例包括Na+、K+、Li+或銨鹽。
更詳細而言,氧胺化合物可為具有通式(I)之羥胺化合物:
或可為具有通式(II)之胺氧基化合物:
其中R1
及R2
可彼此相同或不同且選自由以下組成之群:氫及直鏈、分支鏈或環烷基、 包括C1
-C8
烷基(例如,甲基、乙基、丙基、丁基、戊基、己基、庚基及辛基)。因此,氧胺化合物可為烷基氧胺(例如烷基羥胺,尤其二烷基羥胺)。適合地,氧胺化合物可為對稱的,其中式(I)及式(II)中之R1
及R2
相同。羥胺化合物之說明性實例包括但不限於羥胺(NH2
OH)、二甲基羥胺、甲基乙基羥胺、甲基丙基羥胺、甲基丁基羥胺、二乙基羥胺(DEHA)、乙基丙基羥胺、乙基丁基羥胺、二丙基羥胺、丙基丁基羥胺、二丁基羥胺、二(第三丁基)羥胺、嗎啉-N-氫氧化物、N-羥基琥珀胺、N-羥基順丁烯二醯亞胺或其鹽。鹽之實例包括但不限於羥胺鹽酸鹽、羥胺硫酸鹽或羥胺乙酸鹽。胺氧基化合物之說明性實例包括但不限於2,2,6,6-四甲基哌啶-1-基)氧基(有時亦稱為(2,2,6,6-四甲基哌啶-1-基)氧烷基或TEMPO)、4-胺基-TEMPO、4-羧基-TEMPO、4-膦基氧基-TEMPO、4-羥基-TEMPO、具有共價鍵結TEMPO側基或端基之聚合物。其他適合之實例包括2,2,5,5-四甲基吡咯啶-1-基(有時亦稱為2,2,5,5-四甲基吡咯啶-N-氧基氮氧化物或PROXYL)、3-胺基-PROXYL、3-羧基-PROXYL、3-膦醯氧基-PROXYL、3-羥基-PROXYL及具有共價鍵結PROXYL側基或端基之聚合物。
在一些實施例中,羥基胺可進一步經官能化,其中例如R1
及R2
可選自由以下組成之群:直鏈或分支鏈C1
-C8
醇(例如甲醇、乙醇、丙醇、丁醇、戊醇、己醇、庚醇及辛醇),及具有式R4
-O-R5
之直鏈或分支鏈醚,其中R4
及R5
可彼此相同或不同且選自由C1
-C8
烷基組成之群,其中R4
或R5
鍵結至N。作為一特定實例,R1
及/或R2
可包含C1
-C4
烷基。
在各種實施例中,按組合物之總重量計,組合物包含在0.1至20% w/w之範圍內之如本文任何地方所描述之氧胺化合物或氧胺化合物組分。適合地,氧胺化合物或氧胺化合物組分的量可在0.01至10% w/w之範圍內,例如在0.1至7% w/w之範圍內。
按清洗組合物之總重量計,清洗組合物中之氧胺化合物或其鹽的量在約0.01 wt%至約25 wt%範圍內。較佳地,按清洗組合物之總重量計,氧胺化合物以約0.1 wt%至約10 wt%的量存在,且更佳以約0.5 wt%至約5 wt%的量存在。
本發明之清洗組合物可視情況進一步包含一或多種額外組分,其可提供其他益處,尤其用於清洗包含含鈷材料之微電子裝置。在一些實施例中,清洗組合物可包含至少一種蝕刻劑、至少一種腐蝕抑制劑及/或至少一種還原劑。
例如,清洗組合物可視情況包含至少一種蝕刻劑。適合地,組合物可包含由複數種額外蝕刻劑組成之蝕刻劑組分。蝕刻劑之實例包括(但不限於)嗎啉、二乙二醇胺、3-丁氧基丙胺、丙二醇單丁醚(例如DOWANOL PnB)、羥乙基嗎啉、羥丙基嗎啉、胺基乙基嗎啉、胺基丙基嗎啉、五甲基二伸乙基三胺(PMDETA)、哌嗪、N,N-二甲基丙醇胺、乙醇胺、二乙醇胺、二乙胺、乙二胺、二伸乙基三胺、四伸乙基五胺、三伸乙基四胺、三甲基胺基乙基乙醇胺、三甲基胺基丙基乙醇胺及其組合。在各種實施例中,按清洗組合物之總重量計,清洗中之蝕刻劑(若存在)的量在約0.1 wt%至約20 wt%之範圍內。較佳地,按組合物之總重量計,蝕刻劑以約1 wt%至約20 wt%的量,且更佳以約1 wt%至約10 wt%的量存在。在各種實施例中,清洗組合物不含有蝕刻劑。
清洗組合物可視情況包含至少一種腐蝕抑制劑。說明性腐蝕抑制劑包括但不限於乙酸、丙酮肟、丙烯酸、己二酸、丙胺酸、精胺酸、天冬醯胺、天冬胺酸、甜菜鹼、二甲基乙二肟、甲酸、反丁烯二酸、葡糖酸、麩胺酸、麩醯胺酸、戊二酸、甘油酸、甘油、乙醇酸、乙醛酸、組胺酸、亞胺二乙酸、間苯二甲酸、伊康酸、乳酸、白胺酸、離胺酸、順丁烯二酸、順丁烯二酸酐、蘋果酸、丙二酸、杏仁酸、2,4-戊二酮、苯乙酸、苯丙胺酸、鄰苯二甲酸、脯胺酸、丙酸、鄰苯二酚、苯均四酸、金雞納酸、絲胺酸、山梨醇、丁二酸、酒石酸、對苯二甲酸、偏苯三甲酸、對稱苯三甲酸、酪胺酸、纈胺酸、木糖醇、草酸、鞣酸、吡啶甲酸、1,3-環戊二酮、兒茶酚、鄰苯三酚、間苯二酚、對苯二酚、三聚氰酸、巴比妥酸、1,2-二甲基巴比妥酸、丙酮酸、丙硫醇、苯并羥肟酸、2,5-二羧基吡啶、4-(2-羥基乙基)嗎啉(HEM)、N-胺基乙基哌嗪(N-AEP)、乙二胺四乙酸(EDTA)、1,2-環己二胺-N,N,N´,N´-四乙酸(CDTA)、N-(羥基乙基)-乙二胺三乙酸(HEdTA)、亞胺二乙酸(IDA)、2-(羥基乙基)亞胺二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、甘胺酸、半胱胺酸、麩胺酸、異白胺酸、甲硫胺酸、哌啶、N-(2-胺基乙基)哌啶、吡咯啶、蘇胺酸、色胺酸、柳酸、對甲苯磺酸、柳基羥肟、5-磺基柳酸、三唑、胺三唑、二甲基丙炔醇、月桂醯基肌胺酸、硬脂醯基肌胺酸、糖精及其組合。在各種實施例中,按清洗組合物之總重量計,清洗中之腐蝕抑制劑(若存在)的量在約0.01 wt%至約10 wt%之範圍內。較佳地,按組合物之總重量計,腐蝕抑制劑以約0.01 wt%至約5 wt%的量存在,且更佳以約0.05 wt%至約5 wt%的量存在。在各種實施例中,清洗組合物不含有腐蝕抑制劑。
清洗組合物可視情況包含至少一種還原劑。說明性還原劑包括但不限於抗壞血酸、L(+)-抗壞血酸、異抗壞血酸、抗壞血酸衍生物、亞硫酸、亞硫酸銨、亞硫酸鉀、亞硫酸鈉、多巴胺HCl、亞磷酸、次膦酸、次膦酸、偏亞硫酸氫鉀、偏亞硫酸氫鈉、偏亞硫酸氫銨、丙酮酸鉀、丙酮酸鈉、丙酮酸銨、甲酸、甲酸鈉、甲酸鉀、甲酸銨、多巴胺、二氧化硫溶液及其任何組合。例如,至少一種還原劑可包含至少一種亞硫酸離子及至少一種其他所枚舉之還原劑,例如亞硫酸、亞硫酸鉀、亞硫酸銨、次膦酸及其任何組合。應瞭解當存在亞硫酸銨時,可當場產生亞硫酸銨,其中特定組分之組合導致形成亞硫酸銨以輔助移除殘留物,例如二氧化鈰粒子及其他CMP後殘留物。在各種實施例中,按清洗組合物之總重量計,清洗中之還原劑(若存在)的量在約0.0001 wt%至約1 wt%之範圍內。較佳地,按組合物之總重量計,還原劑以約0.0001 wt%至約0.2 wt%的量,且更佳以約0.01 wt%至約0.2 wt%的量存在。在各種實施例中,清洗組合物不含有還原劑。
組分之重量百分比比率範圍將覆蓋組合物之所有可能經濃縮或經稀釋之實施例。朝向該目的,在一個實施例中,經濃縮之移除組合物限制條件為可稀釋以用作清洗溶液。濃縮組合物或「濃縮物」有利地准許使用者(例如CMP製程工程師)在使用時將濃縮物稀釋至所需強度及pH。經濃縮之水性移除組合物之稀釋可在約1:1至約2500:1、較佳約5:1至約200:1且最佳約20:1至約120:1之範圍內,其中水性移除組合物在工具處或恰好在工具之前經溶劑(例如去離子水)稀釋。熟習此項技術者應瞭解,在稀釋之後,本文所揭示之組分之重量百分比之範圍應保持不變。
本文中所描述之組合物可在包括但不限於蝕刻後殘留物移除、灰化後殘留物移除表面製備、電鍍後清洗及CMP後殘留物去除之應用中具有效用。除了清洗含鈷組分以外,預期本文中所描述之水性清洗組合物亦可適用於清洗及保護其他金屬(例如,含銅及含鎢)產物,包括但不限於使用金屬或金屬合金之裝飾性金屬、金屬線接合、印刷電路板及其他電子封裝。
水性移除組合物藉由簡單添加相應成分且混合至均質狀況容易地調配出。此外,組合物可易於調配為單封裝調配物或在使用時或使用前混合之多部分調配物,例如,多部分調配物之個別部分可在工具處或在工具上游之儲槽中混合。各別成分之濃度可以組合物之特定倍數廣泛變化,亦即更稀或更濃,且應瞭解,本文中所描述之組合物可不同地且可替代地包含符合本文中之揭示內容之成分的任何組合、由其組成或基本上由其組成。
因此,另一態樣係關於一種套組,該套組在一或多個容器中包括經調適以形成本文中所描述之清洗組合物之一或多種組分。套組在一或多個容器中可包括至少一種錯合劑、至少一種清洗添加劑、至少一種pH調節劑、至少一種氧胺化合物、水、視情況選用之至少一種蝕刻劑、視情況選用之至少一種腐蝕抑制劑及視情況選用之至少一種還原劑,用於在製造時或在使用時與額外溶劑(例如,水)組合。替代地,套組在一或多個容器中可包括至少一種錯合劑、至少一種清洗添加劑、至少一種氧胺化合物、水、視情況選用之至少一種蝕刻劑、視情況選用之至少一種腐蝕抑制劑及視情況選用之至少一種還原劑,用於在製造時或在使用時與至少一種pH調節劑及額外溶劑(例如,水)組合。套組之容器必須適合於儲存及運送組合物,且可為例如NOWPak®容器(Entegris, Inc., Billerica, Mass., USA)。
含有水性清洗組合物之組分的一或多個容器較佳包括用於使該一或多個容器中之組分流體連通以便摻合及分配的構件。例如,參考NOWPak®容器,可向該等一或多個容器中內襯之外部施加氣體壓力以使得內襯之內容物的至少一部分釋放且因此使得能夠流體連通以便摻合及分配。替代地,可向可用於使得能夠實現流體連通之習知可加壓容器或泵的頂部空間施加氣體壓力。另外,系統較佳包括用於將經摻合移除組合物分配至處理工具之施配口。
當應用於微電子製造操作時,有效地採用本文所描述之清洗組合物以自微電子裝置之表面移除包括粒子、CMP後殘留物、灰化後殘留物及蝕刻後殘留物之殘留物及污染物。有利地,本文中所描述之本發明清洗組合物相對於此項技術中先前所描述之替代性清洗組合物展示經改良之鈷相容性。因此,本發明進一步係關於使用本文中所描述之清洗組合物自上面有殘留物及污染物之微電子裝置移除該等殘留物及污染物的方法。
該方法包含使微電子裝置與清洗組合物接觸足以至少部分地自微電子裝置清洗該等殘留物及污染物的時間,在使用中,在約20℃至約90℃、較佳約20℃至約50℃之範圍內之溫度下,使清洗組合物典型地與裝置接觸約5秒至約10分鐘、較佳約1秒至20分鐘、較佳約15秒至約5分鐘之時間。此類接觸時間及溫度為說明性的,且在該方法之廣泛實踐內,可採用有效地自裝置至少部分移除殘留物及污染物之任何其他適合的時間及溫度條件。「至少部分清洗」及「實質上移除」均對應於在粒子移除之前移除存在於裝置上之至少85%、更佳至少90%、甚至更佳至少95%或最佳至少99%之氧化鈰粒子。
在接觸裝置及移除目標所需殘留物及/或污染物之後,清洗組合物可易於自先前已施加有該清洗組合物之裝置移除,如在本文所描述之組合物之既定最終用途應用中可為所需且有效的。例如,較佳可使用沖洗溶液,其中沖洗溶液包括去離子水。其後,如此項技術中已知,可使用氮氣或旋轉乾燥循環來乾燥裝置。
本發明之又一態樣係關於根據本文所描述之方法製得之經改良微電子裝置且關於含有此類微電子裝置之產物。另一態樣係關於一種再循環清洗組合物,其中如熟習此項技術者容易地確定,該組合物可經再循環直至粒子及/或污染物負載達至水性移除組合物可容納之最大量為止。因此,本文中所揭示之清洗組合物可包括殘留物及/或污染物。殘餘物及污染物可溶解於組合物中。替代地,殘餘物及污染物可懸浮於組合物中。較佳地,殘留物包括CMP後殘留物、蝕刻後殘留物、灰化後殘留物、污染物或其組合。又一態樣係關於製造包含微電子裝置之物品的方法,該方法包含使該微電子裝置與本發明清洗組合物接觸,持續足以自該微電子裝置移除殘餘物及/或污染物之時間,且將該經清洗之微電子裝置併入至該物品中。另一態樣係關於藉由此方法產生之物品。實例
除非另外明確說明,否則本發明之清洗組合物之特徵及優點藉由以下非限制性實例更充分地說明,其中所有份數及百分比均按重量計。所揭示之清洗組合物尤其適用於自微電子裝置結構清洗殘留物及污染物(例如CMP後殘留物、蝕刻後殘留物、灰化後殘留物及污染物)同時仍與存在於表面上之含鈷材料相容。實例 1
以下實例表明將至少一種羥胺添加至清洗組合物之有效性。
製備兩種組合物且展示於下表1中。表中之所有數值均指按總組合物計之wt%,且總計100%之任何失敗僅歸因於捨入。
表1
ID | 去離子水 | 46.7% 氫氧化膽鹼溶液 | MEA | 半胱胺酸 | DEHA | L- 酒石酸 | 蝕刻速率 (A/min) | 蝕刻速率標準差 |
比較實例1 | 80.5 | 18.2 | 1.1 | 0.05 | 0 | 0.095 | 0.6 | 0.02 |
實例1 | 75.6 | 18.2 | 1.1 | 0.05 | 4.9 | 0.095 | 0.4 | 0.05 |
如所展示,比較實例1與實例1之組合物之間的唯一差異為用DEHA置換一定量之水。比較實例1為不根據本發明之比較實例。
各組合物以60:1水與組合物之比率經去離子水稀釋,且隨後在30℃之溫度下將鈷之試樣暴露於各經稀釋之組合物15分鐘。測定鈷試樣之蝕刻程度且展示於表1中。如可見,比較實例1之清洗組合物展示0.6 A/min之蝕刻速率且標準差為0.02。經比較,實例1之組合物展示0.4 A/min之蝕刻速率且標準差為0.05。此等結果展示包括諸如DEHA之羥胺有效地減少鈷蝕刻。實例 2-3
以下實例展現本發明之清洗組合物,其包含至少一種羥胺且具有高鈷相容性。
製備包含至少一種錯合劑、至少一種清洗添加劑、至少一種pH調節劑及至少一種羥胺之本發明組合物。組合物如下:實例 2
:18.2%氫氧化膽鹼(作為46.7%水溶液添加)、1.13% MEA、0.05%半胱胺酸、4.9% DEHA及75.625%去離子水。組合物之pH為13.5。實例 3
:2.09% KOH(作為45%水溶液添加)、1.25% MEA、0.1%半胱胺酸、0.8% HEDP(作為60%水溶液添加)、5.3%嗎啉、1% 1-丁氧基-2-丙醇、3% DMSO、0.9% DEHA及85.56%去離子水。
所有數值均指按總組合物計之wt%,且總計100%之任何失敗僅歸因於捨入。
各組合物以60:1水與組合物之比率經去離子水稀釋。隨後在30℃之溫度下將鈷之試樣暴露於各經稀釋之組合物15分鐘且測定鈷試樣之蝕刻程度。已發現含有DEHA作為羥胺之實例2及實例3兩者之組合物基於其減小之鈷蝕刻速率而具有經改良之鈷相容性。實例 4-13
以下實例表明本發明之各種清洗組合物之有效性,該等清洗組合物包含至少一種用於自鈷基板移除二氧化矽漿料之羥胺。
製備包含至少一種錯合劑、至少一種清洗添加劑、至少一種pH調節劑及至少一種羥胺之本發明之組合物且展示於下表2中。表中之所有數值均指按總組合物計之wt%,且總計100%之任何失敗僅歸因於捨入。
製備所展示之組合物且經水稀釋100:1。將鈷試樣浸沒於含二氧化矽漿料中5分鐘,在去離子水中沖洗30秒,且隨後浸沒於清洗組合物中60秒,隨後經第二次去離子水沖洗液沖洗30秒。浸沒期間之溫度為室溫。使用掃描電子顯微法(SEM)測定清洗程度,且結果展示於下表3中。
表2
表3
實例 | 去離子水 | 45% KOH | MEA | 半胱胺酸 | 嗎啉 | HEDP | DEHA | DMSO | 1- 丁氧基 -2- 丙醇 | 亞硫酸 |
4 | 83.01 | 4.64 | 1.25 | 0.1 | 5.3 | 0.8 | 0.9 | 3 | 1 | 0 |
5 | 78.31 | 4.64 | 4.95 | 0.2 | 5.3 | 0.8 | 1.8 | 3 | 1 | 0 |
6 | 83.46 | 4.64 | 0 | 0 | 5.3 | 0.8 | 1.8 | 3 | 1 | 0 |
7 | 78.51 | 4.64 | 4.95 | 0 | 5.3 | 0.8 | 1.8 | 3 | 1 | 0 |
8 | 83.26 | 4.64 | 0 | 0.2 | 5.3 | 0.8 | 1.8 | 3 | 1 | 0 |
9 | 85.75 | 1.9 | 1.25 | 0.1 | 5.3 | 0.8 | 0.9 | 3 | 1 | 0 |
10 | 85.75 | 1.9 | 1.25 | 0.1 | 5.3 | 0.8 | 0.9 | 3 | 1 | 0.1 |
11 | 85.75 | 1.9 | 1.25 | 0.1 | 5.3 | 0.8 | 0.9 | 3 | 1 | 0.4 |
12 | 86.15 | 1.9 | 1.25 | 0.1 | 5.3 | 0.4 | 0.9 | 3 | 1 | 0.1 |
13 | 86.15 | 1.9 | 1.25 | 0.1 | 5.3 | 0.4 | 0.9 | 3 | 1 | 0.4 |
實例 | 二氧化矽粒子 (SEM) |
2 | 3308 |
3 | 2737 |
4 | 2789 |
5 | 4540 |
6 | 4508 |
7 | 3008 |
8 | 5490 |
9 | 3137 |
10 | 6950 |
11 | 5470 |
如所示,含有二乙基羥胺之清洗組合物中之各者能夠有效地自含鈷基板移除二氧化矽漿液粒子。因此,含有羥胺之組合物可自鈷基板移除殘餘物粒子同時維持有效的鈷相容性(如藉由實例1-3中之減小之蝕刻速率所展示)。
儘管本文已參考說明性實施例及特徵不同地揭示本發明,但應瞭解上文描述之實施例及特徵不意欲限制本發明,且基於本文中揭示內容,其他變化、修飾及其他實施例將向彼等一般技術者表明自身。因此如在下文闡述之申請專利範圍的精神及範疇內涵蓋所有此類變化、修飾及替代實施例,將大致解釋本發明。
Claims (10)
- 一種用於自上面有殘留物及污染物之微電子裝置清洗該等殘留物及污染物的清洗組合物,該清洗組合物包含至少一種錯合劑、至少一種清洗添加劑、至少一種pH調節劑、水及至少一種氧胺化合物或其鹽。
- 如請求項1之清洗組合物,其中該錯合劑包含選自由以下組成之群的物種:胺基乙基乙醇胺、N-甲基胺基乙醇、胺基乙氧基乙醇、二甲基胺基乙氧基乙醇、二乙醇胺、N-甲基二乙醇胺、單乙醇胺(MEA)、三乙醇胺(TEA)、異丙醇胺、二異丙醇胺、胺基丙基二乙醇胺、N,N-二甲基丙醇胺、N-甲基丙醇胺、1-胺基-2-丙醇、2-胺基-1-丁醇、異丁醇胺、三伸乙基二胺、 4-(2-羥基乙基)嗎啉(HEM)、1,2-環己二胺-N,N,N',N'-四乙酸(CDTA)、乙二胺四乙酸(EDTA)、間二甲苯二胺(MXDA)、亞胺二乙酸(IDA)、2-(羥基乙基)亞胺二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、尿酸、丙胺酸、精胺酸、天冬醯胺、天冬胺酸、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、苯丙胺酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸、1-羥基亞乙基-1,1-二膦酸(HEDP)、 1,5,9-三氮雜環十二烷-N,N',N''-參(亞甲基膦酸)(DOTRP)、1,4,7,10-四氮雜環十二烷-N,N,N'',N'''-肆(亞甲基膦酸)(DOTP)、氮基參(亞甲基)三膦酸、二伸乙基三胺五(亞甲基膦酸)(DETAP)、胺基三(亞甲基膦酸)、雙(伸己基)三胺伸戊基膦酸、1,4,7-三氮雜環壬烷-N,N',N''-參(亞甲基膦酸(NOTP)、羥基乙基二膦酸酯、氮基參(亞甲基)膦酸、 2-膦醯基-丁烷-1,2,3,4-四甲酸、羧基乙基膦酸、胺基乙基膦酸、草甘膦、乙二胺四(亞甲基膦酸)苯基膦酸、草酸、丁二酸、順丁烯二酸、蘋果酸、丙二酸、己二酸、鄰苯二甲酸、檸檬酸、檸檬酸鈉、檸檬酸鉀、檸檬酸銨、1,2,3-丙三羧酸、三羥甲基丙酸、酒石酸、葡萄糖醛酸、2-羧基吡啶、4,5-二羥基-1,3-苯二磺酸二鈉鹽及其組合。
- 如請求項1之清洗組合物,其中該清洗添加劑包含選自由以下組成之群的物種:2-吡咯啶酮、1-(2-羥基乙基)-2-吡咯啶酮(HEP)、甘油、1,4-丁二醇、伸丁基碸(環丁碸)、二甲碸、乙二醇、丙二醇、二丙二醇、四乙二醇二甲醚、二乙二醇二甲醚、甲基異丁基酮、甲基乙基酮、丙酮、異丙醇、辛醇、乙醇、丁醇、甲醇、異佛爾酮、二醇醚(例如二乙二醇單甲醚、三乙二醇單甲醚、二乙二醇單乙醚、三乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、 二乙二醇單丁醚(DEGBE)、三乙二醇單丁醚(TEGBE)、乙二醇單己醚(EGHE)、二乙二醇單己醚(DEGHE)、乙二醇苯醚、二乙二醇苯醚、六乙二醇單苯醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二丙二醇二甲醚、二丙二醇乙醚、丙二醇正丙醚、二丙二醇正丙醚(DPGPE)、三丙二醇正丙醚、丙二醇正丁醚(諸如DOWANOL PnB)、二丙二醇正丁醚、三丙二醇正丁醚、二丙二醇苯醚、丙二醇苯醚(PPh,諸如DOWANOL PPh)、 4-甲基-2-戊酮、2,4-二甲基-3-戊酮、環己酮、5-甲基-3-庚酮、3-戊酮、5-羥基-2-戊酮、2,5-己二酮、4-羥基-4-甲基-2-戊酮、丙酮、丁酮、2-甲基-2-丁酮、3,3-二甲基-2-丁酮、4-羥基-2-丁酮、環戊酮、2-戊酮、3-戊酮、1-苯基乙酮、苯乙酮、二苯甲酮、2-己酮、3-己酮、2-庚酮、3-庚酮、4-庚酮、2,6-二甲基-4-庚酮、2-辛酮、3-辛酮、4-辛酮、二環己基酮、2,6-二甲基環己酮、2-乙醯基環己酮、2,4-戊二酮、薄荷酮、二甲亞碸(DMSO)、二甲基甲醯胺(DMF)、N-甲基吡咯啶酮、N-乙基吡咯啶酮、 羥基丙基纖維素、羥基乙基纖維素、羧甲基纖維素、羧甲基纖維素鈉(NaCMC)、十二烷基硫酸鈉(SDS);Surfynol 104、聚乙烯吡咯啶酮(PVP)、聚胺基酸、聚醯胺羥基胺基甲酸酯、聚內酯、聚丙烯醯胺、三仙膠、聚葡萄胺糖、聚氧化乙烯、聚乙烯醇、聚乙酸乙烯酯、聚丙烯酸、聚乙亞胺、山梨醇酯、木糖醇、去水山梨醇之酯、二級醇乙氧基化物、海藻酸鉀、海藻酸銨、聚(乙二醇甲基丙烯酸酯)及其組合。
- 如請求項1之清洗組合物,其中該pH調節劑包含選自由以下組成之群的物種:鹼金屬氫氧化物、鹼土金屬氫氧化物、氫氧化銨、氫氧化四甲銨(TMAH)、氫氧化四乙基銨(TEAH)、氫氧化四丙基銨(TPAH)、氫氧化四丁基銨(TBAH)、氫氧化三丁基甲銨(TBMAH)、氫氧化苄基三甲銨(BTMAH)、氫氧化膽鹼、氫氧化乙基三甲銨、氫氧化參(2-羥基乙基)甲銨、氫氧化二乙基二甲銨、氫氧化四丁基鏻(TBPH)、氫氧化四甲基鏻、氫氧化四乙基鏻、氫氧化四丙基鏻、氫氧化苄基三苯基鏻、氫氧化甲基三苯基鏻、氫氧化乙基三苯基鏻、氫氧化正丙基三苯基鏻及其組合。
- 如請求項1之清洗組合物,其中該清洗組合物進一步包含至少一種蝕刻劑,其中該蝕刻劑包含選自由以下組成之群的物種:嗎啉、二乙二醇胺、3-丁氧基丙胺、丙二醇單丁醚(DOWANOL PnB)、羥乙基嗎啉、羥丙基嗎啉、胺基乙基嗎啉、胺基丙基嗎啉、五甲基二伸乙基三胺(PMDETA)、哌嗪、N,N-二甲基丙醇胺、乙醇胺、二乙醇胺、二乙胺、乙二胺、二伸乙基三胺、四伸乙基五胺、三伸乙基四胺、三甲基胺基乙基乙醇胺、三甲基胺基丙基乙醇胺及其組合。
- 如請求項1之清洗組合物,其中該清洗組合物進一步包含至少一種腐蝕抑制劑,其中該腐蝕抑制劑包含選自由以下組成之群的物種:乙酸、丙酮肟、丙烯酸、己二酸、丙胺酸、精胺酸、天冬醯胺、天冬胺酸、甜菜鹼、二甲基乙二肟、甲酸、反丁烯二酸、葡糖酸、麩胺酸、麩醯胺酸、戊二酸、甘油酸、甘油、乙醇酸、乙醛酸、組胺酸、亞胺二乙酸、間苯二甲酸、伊康酸、乳酸、白胺酸、離胺酸、順丁烯二酸、順丁烯二酸酐、蘋果酸、丙二酸、杏仁酸、2,4-戊二酮、苯乙酸、苯丙胺酸、鄰苯二甲酸、脯胺酸、丙酸、 鄰苯二酚、苯均四酸、金雞納酸、絲胺酸、山梨醇、丁二酸、酒石酸、對苯二甲酸、偏苯三甲酸、對稱苯三甲酸、酪胺酸、纈胺酸、木糖醇、草酸、鞣酸、吡啶甲酸、1,3-環戊二酮、兒茶酚、鄰苯三酚、間苯二酚、對苯二酚、三聚氰酸、巴比妥酸、1,2-二甲基巴比妥酸、丙酮酸、丙硫醇、苯并羥肟酸、2,5-二羧基吡啶、4-(2-羥基乙基)嗎啉(HEM)、N-胺基乙基哌嗪(N-AEP)、乙二胺四乙酸(EDTA)、 1,2-環己二胺-N,N,N´,N´-四乙酸(CDTA)、N-(羥基乙基)-乙二胺三乙酸(HEdTA)、亞胺二乙酸(IDA)、2-(羥基乙基)亞胺二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、甘胺酸、半胱胺酸、麩胺酸、異白胺酸、甲硫胺酸、哌啶、N-(2-胺基乙基)哌啶、吡咯啶、蘇胺酸、色胺酸、柳酸、對甲苯磺酸、柳基羥肟、5-磺基柳酸、三唑、胺基三唑、二甲基丙炔醇、月桂醯基肌胺酸、硬脂醯基肌胺酸、糖精及其組合。
- 如請求項1之清洗組合物,其中該清洗組合物進一步包含至少一種還原劑,其中該還原劑包含選自由以下組成之群的物種:抗壞血酸、L(+)-抗壞血酸、異抗壞血酸、抗壞血酸衍生物、亞硫酸、亞硫酸銨、亞硫酸鉀、亞硫酸鈉、多巴胺HCl、亞磷酸、次膦酸、偏亞硫酸氫鉀、偏亞硫酸氫鈉、偏亞硫酸氫銨、羥胺、丙酮酸鉀、丙酮酸鈉、丙酮酸銨、甲酸、甲酸鈉、甲酸鉀、甲酸銨、多巴胺、二氧化硫溶液及其組合。
- 一種自上面有殘留物及污染物之微電子裝置移除該等殘留物及污染物的方法,該方法包含使該微電子裝置與清洗組合物接觸足以至少部分地自該微電子裝置清洗該等殘留物及污染物的時間,其中該清洗組合物包含至少一種錯合劑、至少一種清洗添加劑、至少一種pH調節劑、水及至少一種氧胺化合物或其鹽。
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JP2022514611A (ja) | 2022-02-14 |
KR102625498B1 (ko) | 2024-01-17 |
US20200199500A1 (en) | 2020-06-25 |
US11845917B2 (en) | 2023-12-19 |
WO2020131313A1 (en) | 2020-06-25 |
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